Water-in-oil-in-water compositions

ABSTRACT

Water-in-oil-in-water multiple emulsion compositions are disclosed. The multiple emulsion compositions comprise an external aqueous phase optionally incorporating a surfactant system capable of forming liquid crystals as an emulsifier. The internal phase comprises a primary water-in-oil emulsion, wherein the primary emulsion comprises a first topically-active compound, a surfactant phase, an oil phase, and water.

FIELD OF THE INVENTION

The present invention is directed to water-in-oil-in-water (W₁ -O-W₂)multiple emulsion compositions comprising: (1) a primary water-in-oil(W₁ /O) emulsion as the internal phase and (2) an external aqueousphase. The primary W₁ /O emulsion comprises (a) a first topically-activecompound; (b) a surfactant or blend of surfactants; (c) an oil phasecomprising a silicone compound, a hydrocarbon compound or a mixturethereof; and (d) water. The external aqueous phase comprises water andan emulsifier comprising a surfactant system capable of formingstabilizing liquid crystals. The external aqueous phase preferablyfurther comprises a second topically-active compound. In use, a W₁ -O-W₂multiple emulsion composition is applied to the skin or hair to deliverthe second topically-active compound. The external aqueous phase of thecomposition can be rinsed from or allowed to remain on the skin or hair.The primary (W₁ /O) emulsion deposits on and remains on the hair orskin. After evaporation of the oil phase or after rupture of the W₁ /Oemulsion by friction (e.g., rubbing), the first topically-effectivecompound remains on the skin or hair to perform its intended function.

BACKGROUND OF THE INVENTION

An ideal composition for delivery of a topically-active compound to skinor hair delivers the topically-active compound such that it adheres tothe skin or hair, while topically-inactive ingredients evaporate or arerinsed from the application site. Delivery of a water-insolubletopically-active compound is facilitated because the topically-activecompound is not removed from the application site during the rinsingstep. The difficulty with this type of composition resides inincorporating the water-insoluble topically-active compound into anaqueous composition. This difficulty is overcome by forming emulsions.Therefore, topically-active compounds, such as a hair conditioner, ahair dye, a skin care compound or a topical medicament, conventionallyhave been delivered from either oil-in-water emulsions or water-in-oilemulsions.

With respect to water-soluble and water-dispersible topically-activecompounds (hereinafter collectively termed "water-solubletopically-active compounds"), it is easy to incorporate thetopically-active compound into an aqueous composition. However, asubstantial amount, or all, of the water-soluble compound can be rinsedfrom the treated skin or hair. The water-soluble compound thereforecannot perform its intended function and is wasted. Accordingly,rinse-off compositions often incorporate an excess of the water-solubletopically-active compound, such that a sufficient amount of the compoundremains on the skin or hair after rinsing to perform its intendedfunction. This problem is not encountered with leave-on compositions.

Similarly, two-in-one products, like shampoo-conditioner compositions,have been difficult to formulate not only because of the watersolubility of many quaternary ammonium compounds, but also because ofthe well-known incompatibility between an anionic surfactant and aquaternary ammonium compound. Formulators either have avoided thisproblem by sequentially contacting the hair first with an anionicsurfactant composition, then a quaternary ammonium compound composition,or have overcome this problem by using silicone conditioners inshampoo-conditioners. However, silicones and similar conditioners arewater insoluble and an esthetically-unpleasant residue builds up on thehair after repeated applications. In addition, quaternary ammoniumcompounds impart hair conditioning properties different from a silicone,and therefore it is desirable to condition the hair with quaternaryammonium compounds in place of, or in conjunction with, a silicone.

Investigators therefore have searched for topically-effectivecompositions that overcome the above-described disadvantages, and thathave consumer-acceptable stability and esthetics. Rinse-off,topically-effective compositions however often are difficult toformulate because of the water solubility of the desiredtopically-active compound. Leave-on, topically effective compositionsare difficult to formulate because of the incompatibility betweenvarious topically-active compositions.

One type of composition that has been investigated to overcome theseproblems are multiple emulsions. Multiple emulsions are complexemulsions of emulsions formed by dispersing droplets in a continuousphase, wherein the droplets themselves contain smaller droplets of aliquid similar to the external continuous phase. One type of multipleemulsion is a water-in-oil-in-water emulsion (W₁ -O-W₂), wherein aprimary water-in-oil (W₁ /O) emulsion is dispersed in an externalaqueous phase (W₂). Multiple emulsions also are known as liquid membranesystems because, in the case of a W₁ -O-W₂ emulsion, an organicmembrane, film or layer separates the inner water droplets from theexternal aqueous phase.

W₁ -O-W₂ multiple emulsion compositions have been used in thepharmaceutical industry as vaccine adjuvants and as sustained releaseand parental drug delivery systems. However, the low stability of W₁-O-W₂ multiple emulsion compositions has limited their widespread use.

Multiple emulsion compositions also have been used in cosmetics and skincare products. W₁ -O-W₂ multiple emulsions however were difficult toprepare and were unstable at elevated temperatures. In addition, variousactive ingredients had a tendency to further destabilize the multipleemulsions, for example causing leakage between the external aqueousphase and internal aqueous phase.

W₁ -O-W₂ multiple emulsion compositions have been disclosed in numerouspatents and publications. For example, M. C. Taelman et al., "MultipleEmulsions in Cosmetics", Publication RP112/94E, March, 1994, ICI EuropeLimited, Everberg, Belgium, discloses multiple emulsions in general,including methods of manufacturing multiple emulsions. S. Matsumoto etal., J. Dispersion Science and Technology, 10 (1989), pp. 455-482,discloses the use of multiple emulsions in the food, drug and cosmeticindustries.

Other publications which disclose multiple W₁ -O-W₂ emulsions are:

S. S. Davis et al., Encyclopedia of Emulsion Technology, Vol. 2; P.Becher, Ed.; Marcel Dekker, Inc., New York, N.Y. (1985), pp. 159-238;

Y. Sela et al., Colloids and Surfaces A: Physicochemical and EngineeringAspects, 83 (1994), pp. 143-150;

K. Oza et al., J. Dispersion Science and Technology, 10(2) (1985), pp.163-185;

J. Zatz et al., J. Soc. Cosmet. Chem., 39 (May/June 1988), pp. 211-222;

C. Fox, Cosmetics and Toiletries, 101 (Nov. 1986), pp. 101-106 and109-112;

M. deluca et al., Cosmetics and Toiletries, 105 (Nov. 1990), pp. 65-66and 69;

T. Tadros, "Application of Multiple Emulsions in Cosmetics", ICISurfactant publication RP56/92E (1992); and

C. Prybilsky et al., Cosmetics and Toiletries, 106 (Nov. 1991), pp.97-100.

Various patents disclose multiple emulsion compositions used in cosmeticcompositions. For example, WO 94/01073 discloses gelled multipleemulsion compositions for cosmetic use. Other patents include WO94/02120; WO 93/00160; WO 92/18227; JP 58 183 611; U.S. Pat. No.5,306,498; and U.S. Pat. No. 4,988,456.

U.S. Pat. Nos. 5,277,899 and 4,963,348, and WO 93/07848, discloseconditioners that have set retention properties. The disclosedcompositions are oil-in-water emulsions (O/W), as opposed to the presentW₁ /O primary emulsions and the W₁ -O-W₂ multiple emulsion compositions.

Although various patents and publications disclose W₁ -O-W₂ multipleemulsion compositions for cosmetic use, those compositions lack thestability needed for a consumer-acceptable topically-effectivecomposition. The present invention therefore is directed to stable W₁-O-W₂ multiple emulsion compositions which are capable of depositingwater-soluble, topically-active compounds onto hair or skin fromcompositions, such as hair conditioners, hair shampoos, or skincleaners.

SUMMARY OF THE INVENTION

The present invention is directed to topically-effective W₁ -O-W₂multiple emulsion compositions having improved stability and efficacy,and to methods of using the W₁ -O-W₂ multiple emulsion compositions.More particularly, the present invention is directed to a W₁ -O-W₂multiple emulsion composition comprising a continuous external aqueousphase (W₂) and a primary water-in-oil (W₁ /O) emulsion as the dispersedinternal phase. The primary W₁ /O emulsion is emulsified in the externalaqueous phase by a surfactant system that is capable of forming a layerof lamellar liquid crystals around droplets of the primary emulsion.

The primary W₁ /O emulsion comprises a first topically-active compound,like a hair conditioner, a hair dye, a hair fixative, a skin carecompound or a topical medicament; a surfactant phase comprisingsilicon-free surfactant or surfactant blend having an HLB value of about10 or less, an oil-soluble silicon-based surfactant, an oil-solublepolymeric surfactant or a mixture thereof; an oil phase comprising asilicone compound or a hydrocarbon compound; and water. The externalphase comprises water, a surfactant system capable of formingstabilizing liquid crystals, and preferably a second topically-activecompound.

In particular, the W₁ -O-W₂ multiple emulsion compositions comprise:

(a) about 40% to about 99% by weight of the composition of an externalaqueous phase (W₂); and

(b) about 1% to about 60% by weight of the composition of a primary W₁/O emulsion.

The primary W₁ /O emulsion comprises:

(a) about 1% to about 95% by weight of the primary emulsion of anaqueous phase comprising (i) a first topically-active compound and (ii)water;

(b) about 0.5% to about 95% by weight of the primary emulsion of an oilphase comprising a volatile silicone compound, a nonvolatile siliconecompound, a volatile hydrocarbon compound, a nonvolatile hydrocarboncompound, or a mixture thereof; and

(c) about 0.1% to about 20% by weight of the primary emulsion of asurfactant phase comprising a silicon-free surfactant or surfactantblend having an HLB value of about 10 or less, an oil-solublesilicon-based surfactant, an oil-soluble polymeric surfactant, or amixture thereof.

The external aqueous phase (W₂) includes a surfactant system capable offorming stabilizing liquid crystals as an emulsifier, and optionallyincludes a second topically-active compound which can perform the sameor a different function from the first topically-active compound.

A W₁ -O-W₂ multiple emulsion composition of the present invention can bea liquid composition having a viscosity of about 1 cps to about 15,000cps (centipoise), and preferably about 100 to about 10,000 cps. Toachieve the full advantage of the present invention, a liquidtopically-effective composition has a viscosity of about 1,000 to about9,000 cps. The W₁ -O-W₂ multiple emulsion also can be cream-like andhave a viscosity of about 50,000 to about 1,200,000 cps, and preferablyabout 100,000 to about 1,000,000 cps.

The W₁ -O-W₂ multiple emulsion compositions of the present inventionare: (1) leave-on compositions, which are designed for application tothe skin or hair without a subsequent rinsing step or (2) rinse-offcompositions, which are designed for application to the skin or hair,followed by rinsing from the skin or hair. For either type ofcomposition, the second topically-active compound, if present in theexternal aqueous phase, performs its intended function during and aftertopical application of the composition to the skin or hair. If thecomposition is a rinse-off composition, the droplets of the primary W₁/O emulsion are of sufficient size, i.e., a range of about 5 to about1000 μ (microns), and preferably about 10 to about 500 μ, in diameter,to resist removal from the skin or hair during the rinsing step. Thedroplets of the internal W₁ phase of the W₁ /O primary emulsion range insize from about 1 to about 75 μ.

For either a leave-on or a rinse-off composition, the external oil phaseof the primary W₁ /O emulsion then can evaporate during drying of theskin or hair to release the first topically-active compound present inthe internal aqueous phase of the primary emulsion. Alternatively, theinternal aqueous phase is released by rubbing the skin or hair to breakthe W₁ /O primary emulsion. The first topically-active compound then cancontact the skin or hair to perform its intended function. In anotherembodiment, the primary W₁ /O emulsion is not broken, but is allowed toremain on the skin or hair as is. Typically, the first topically-activecompound is not rinsed from the skin or hair.

In accordance with an important aspect of the present invention, awater-soluble (or water-dispersible), topically-active compoundtherefore can be incorporated into a rinse-off composition withoutwasting a substantial amount of the topically-active compound during therinsing step.

Another important aspect of the present invention is the ability totreat the skin or hair with incompatible water-soluble, topically-activecompounds using a single W₁ -O-W₂ multiple emulsion composition. Thecomposition can be a rinse-off or a leave-on product. By incorporatingthe first topically-active compound in the internal aqueous phase of theprimary emulsion (W₁) and the second topically-active compound in theexternal aqueous phase of the composition (W₂), the oil phase (O)provides a barrier that separates the two incompatible topically-activecompounds and precludes contact between the compounds. Incompatibletopically-active compounds therefore can be applied to the hair or skinfrom a single composition, as opposed to applying the topically-activecompounds individually from two different compositions.

For example, it is well known that an anionic compound, like an anionicdye, and a cationic compound, like a quaternary ammonium compound, areincompatible. However, these incompatible compounds can be included inthe present W₁ -O-W₂ multiple emulsion compositions.

The quaternary ammonium compound is present as the secondtopically-active compound in the external aqueous phase (W₂). Uponapplication to the hair, the quaternary ammonium compound is substantiveto, and conditions, the hair. The primary W₁ /O emulsion, whichincorporates the anionic dye (i.e., the first topically-active compound)in the aqueous phase, also is present on the hair. The oil phaseprovides further conditioning benefits to the wet hair, and canevaporate during hair drying to release the anionic dye, which colorsthe hair. Similarly, an anionic compound can be the secondtopically-active compound to cleanse the hair and a cationic compoundcan be the first topically-active compound to condition the hair.

In accordance with another important aspect of the present invention,the first topically-active compound is water soluble or waterdispersible. The first topically-active compound therefore can be rinsedfrom the skin or the hair during a subsequent shampooing or rinsing topreclude an undesirable residue of first topically-active compoundbuilding up on the hair.

In another embodiment of the present invention, the first and secondtopically-active compounds are compatible, yet perform differentfunctions. For example, the second topically-active compound can be acleansing compound for the skin or hair, and the first topically-activecompound can be a topical medicament, a hair fixative, or a hair dye,for example.

In another important embodiment, the external aqueous phase does notinclude a second topically-active compound. In this embodiment, thefirst topically-active compound in the primary W₁ /O emulsion isprecluded from contacting the skin or hair until desired. For example,present day water-soluble hair dye compositions stain the hands of theapplicator, sinks and countertops. The present W₁ -O-W₂ multipleemulsion compositions allow application of a water-soluble dye to hair,wherein the dye is released only after the composition is applied to thehair, and the hair is dried. Staining of hands, sinks and countertopstherefore is avoided. Composition economics also is enhanced because thewater-soluble hair dye, a relatively expensive ingredient, is not rinsedfrom the hair and wasted.

In yet another important embodiment, a W₁ -O-W₂ multiple emulsioncomposition of the present invention incorporates a skin cleansing agentor a skin conditioning agent as the second topically-active compound andan astringent salt as the first topically-active compound to form astable and efficacious deodorant-cleanser composition. In otherembodiments of the present invention, the first topically-activecompound is a topically-effective drug or medicament; a topicalanesthetic; a sunscreen agent; a skin care agent; a skin-soothingemollient or other topical cosmetic compound; a topicalanti-inflammatory; and the like.

The first topically-active compound incorporated into the multipleemulsion compositions of the present invention preferably is watersoluble and is incorporated into the aqueous phase of the primary W₁ /Oemulsion. As used herein, the term "water soluble" means "water solubleor water dispersible". However, water-insoluble topically-activecompounds also can be incorporated into the oil phase of the primary W₁/O emulsion.

In a preferred embodiment, the W₁ -O-W₂ multiple emulsion compositionscomprise:

(A) about 50% to about 95% by weight of the composition of an externalaqueous phase, said external aqueous phase comprising:

(i) about 0.1% to about 30% by weight of the external aqueous phase of asecond topically-active compound;

(ii) about 0.5% to about 10% by weight of the external aqueous phase ofa surfactant system capable of forming stabilizing liquid crystals; and

(iii) water;

(B) about 5% to about 50% by weight of the composition of a primarywater-in-oil emulsion, said primary emulsion comprising:

(i) about 10% to about 95% by weight of the primary emulsion of anaqueous phase, said aqueous phase comprising (a) water and (b) atopically-effective amount of a first topically-active compound,typically about 0.1% to about 30% by weight based on the total weight ofthe primary emulsion;

(ii) about 0.5% to about 80% by weight of the primary emulsion of an oilphase comprising a volatile silicone compound, a volatile compound, or amixture thereof; and

(iii) about 0.1% to about 15% by weight of the primary emulsion of asurfactant phase comprising a silicon-free surfactant or surfactantblend having an HLB value of about 1 to about 7, an oil-solublesilicon-based surfactant, an oil-soluble polymeric surfactant or amixture thereof.

Other aspects of the present invention include providing a phase stable,topically-effective composition for the administration of one or morewater-soluble, topically-active compounds to the skin or hair byproviding a primary W₁ /O emulsion having a droplet size of about 5 toabout 1000 μ.

The present W₁ -O-W₂ multiple emulsion compositions are stable overextended storage periods, can be essentially nonstaining, effectivelydeliver one or more water-soluble, topically-active compounds to theskin and hair, and exhibit excellent esthetic and functional propertiesfor consumer acceptance.

The above and other advantages and novel features of the presentinvention will become apparent from the following detailed descriptionof the preferred embodiments.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

A topically-effective composition of the present invention is a stable,W₁ -O-W₂ multiple emulsion comprising an external aqueous phase and aninternal primary emulsion. The primary emulsion comprises a firstwater-soluble, topically-active compound, such as a hair conditioner, ahair fixative, a hair dye or a topical medicament; a surfactant phasecomprising a silicon-free surfactant or surfactant blend having an HLBvalue of about 10 or less, an oil-soluble silicon-based surfactant, anoil-soluble polymeric surfactant, or a mixture thereof; an oil phasecomprising a volatile silicone compound, a nonvolatile siliconecompound, a volatile hydrocarbon compound, a nonvolatile hydrocarboncompound, or a mixture thereof; and water. The external phase compriseswater and a surfactant system capable of forming liquid crystals.

The W₁ -O-W₂ multiple emulsion composition can be a liquid having aviscosity in the range of about 1,000 to about 15,000 cps. The multipleemulsion composition also can be a cream having a viscosity of about50,000 to about 1,200,000 cps.

After application to the skin or hair, the external aqueous phase can berinsed from the skin or hair. Alternatively, a rinsing step can beomitted. In either embodiment, the oil phase of the primary emulsion, ifsufficiently volatile, evaporates during the skin or hair drying processto release the internal aqueous phase of the primary emulsion, therebyallowing the first topically-active compound to contact the skin or hairand perform its intended function. If the oil phase is not volatile, theinternal aqueous phase is released by rubbing the skin or hair to breakthe primary emulsion.

The water-in-oil-in-water multiple emulsion compositions of the presentinvention are designated herein as W₁ -O-W₂ multiple emulsions. Thisdesignation indicates that an oil phase (O) separates an encapsulated,discontinuous aqueous phase (W₁) from a continuous aqueous phase (W₂).Conventionally, the W₁ and W₂ phases differ in compositional make-up,but the W₁ and W₂ phases can be identical.

In accordance with an important feature of the present invention, theliquid W₁ -O-W₂ multiple emulsion compositions are stable compositionsthat effectively resist coalescence of primary W₁ /O droplets over longstorage periods. The W₁ -O-W₂ compositions also resist leakage ortransfer of water-soluble components between the aqueous internal phaseof the primary emulsion (W₁) and the external aqueous phase (W₂). A W₁-O-W₂ multiple emulsion composition generally is available for immediateapplication to the skin or hair without the need to shake or agitate thecomposition in order to redisperse composition ingredients throughoutthe composition prior to use.

In particular, the W₁ -O-W₂ multiple emulsion compositions comprise:

(a) about 40% to about 99% by weight of the composition of an externalaqueous phase; and

(b) about 1% to about 60% by weight of the composition of a primary W₁/O emulsion.

The primary W₁ /O emulsion comprises:

(a) about 1% to about 95% by weight of the primary emulsion of anaqueous phase comprising (i) water and (ii) a topically-effective amountof a first topically-active compound, typically about 0.1% to about 30%by weight of the primary emulsion;

(b) about 0.5% to about 95% by weight of the primary emulsion of an oilphase comprising a volatile silicone compound, a nonvolatile siliconecompound, a volatile hydrocarbon compound, a nonvolatile hydrocarboncompound, or a mixture thereof; and

(c) about 0.1% to about 20% by weight of the primary emulsion of asurfactant phase comprising a silicon-free surfactant or surfactantblend having an HLB value of about 10 or less, and preferably about 7 orless, an oil-soluble silicon-based surfactant, an oil-soluble polymericsurfactant, or a mixture thereof.

The external aqueous phase (W₂) comprises: (a) 0.1% to about 15% basedon the weight of the external aqueous phase of a surfactant systemcapable of forming stabilizing liquid crystals as an emulsifier, andoptionally, (b) a topically-effective amount of a secondtopically-active compound, typically 0% to about 30% by weight of theexternal phase, to perform a function identical to, similar-to ordifferent from the first topically-active compound.

The W₁ -O-W₂ multiple emulsion compositions are stable and exhibitexceptional esthetic and functional properties. The W₁ -O-W₂ multipleemulsion compositions are liquids or creams, and are capable ofeffectively delivering one or more topically-active compounds to theskin or hair from a single composition.

I. The Primary Water-in-Oil (W₁ /O) Emulsion

The primary W₁ /O emulsion comprises water, a first topically-activecompound, an oil phase and a surfactant phase. The water and firsttopically-active compound comprise the aqueous phase of the primary W₁/O emulsion. The primary emulsion comprises droplets containing waterand the first topically-active compound (i.e., the aqueous phase). Thedroplets containing water and the first topically-active compound (W₁)have a diameter ranging from about 1 to about 75 μ and are enveloped bya membrane or film comprising the oil phase and the surfactant phase.The contents of the internal aqueous phase (W₁) therefore do not contactthe external aqueous phase (W₂) of the W₁ -O-W₂ multiple emulsion.

The primary W₁ /O emulsion is present in a W₁ -O-W₂ multiple emulsioncomposition in an amount of about 1% to about 60%, and preferably about5% to about 50%, by weight of the multiple emulsion composition. Toachieve the full advantage of the present invention, the primary W₁ /Oemulsion is present in an amount of about 10% to about 45%, by weight ofthe multiple emulsion composition.

A. The Aqueous Phase

The aqueous phase is the internal phase (W₁) of the primary W₁ /Oemulsion. The internal aqueous phase constitutes about 1% to about 95%by weight of the primary emulsion, and the relatively small amounts ofoil phase and surfactant phase separate the internal aqueous phase (W₁)of the primary emulsion from the external aqueous phase (W₂).

The aqueous phase (W₁) of the present W₁ -O-W₂ multiple emulsioncompositions comprises water and a first topically-active compound. Theaqueous phase can further comprise additional topically-active compoundsand/or optional water-soluble compounds capable of providing a desiredesthetic or functional effect, such as a fragrance.

The aqueous phase (W₁) comprises about 1% to about 95%, and preferablyabout 10% to about 95%, by weight of the primary emulsion. To achievethe full advantage of the present invention, the aqueous phase comprisesabout 25% to about 95% by weight of the primary emulsion. Alternativelyexpressed, the internal aqueous W₁ phase is present in an amount ofabout 0.01% to about 57%, preferably about 0.5% to about 47.5%, and mostpreferably about 2.5% to about 42.75%, by weight of the W₁ -O-W₂multiple emulsion composition.

1. Topically-Active Compounds

In accordance with an important feature of the present invention, a widevariety of topically-active compounds can be incorporated into theaqueous phase of the primary W₁ /O emulsion as the firsttopically-active compound. The topically-active compounds arewater-soluble or water-dispersible and include both cosmetic andmedicinal compounds that act upon contact with the skin or hair. Thefirst topically-active compound is present in a sufficient amount toperform its intended function, typically in an amount of about 0.1% toabout 30% by weight of the primary emulsion, or, alternativelyexpressed, about 0.001% to about 17.1% by weight of the W₁ -O-W₂multiple emulsion composition.

The first topically-active compound typically remains on the skin orhair after application, as opposed to being rinsed from the skin orhair. However, particular first topically-active compounds are designedto be rinsed from the skin or hair after the compound performs itsintended function.

In accordance with an important feature of the present invention, thefirst topically-active compound can be incorporated into the aqueousphase or into the oil phase of the primary emulsion. Whether aparticular first topically-active compound is incorporated into theaqueous phase or the oil phase of the primary emulsion is related to thesolubility of the topically-active composition in water. In preferredembodiments, the first topically-active compound is water soluble and isincorporated into the internal W₁ aqueous phase.

As used herein, the term "water soluble" means water soluble or waterdispersible. A water-soluble compound has a water solubility of at least0.1 g (grams) per 100 ml (milliliters) of water and forms a truesolution. A water-soluble compound can be inherently water soluble orcan be made water soluble by the addition of a solubilizing compound,such as a coupling agent, a co-surfactant, or a solvent. Awater-dispersible compound remains dispersed in water fox at least thetime period necessary to manufacture the primary W₁ /O emulsion, i.e.,at least about one hour.

In addition, the first topically-active compound can be incorporatedinto the aqueous phase and another topically-active compound can beincorporated into the oil phase to achieve enhanced efficacy (e.g., theprimary emulsion includes a medicament in each of the aqueous and oilphases) or to provide different benefits (e.g., the primary emulsionincludes a medicament in the aqueous phase and a topical anesthetic inthe oil phase).

The first topically-active compound therefore can be one of, or acombination of, a cosmetic compound, a medicinally-active compound orany other compound that is useful upon topical application to the skinor hair. Such topically-active compounds include, but are not limitedto, hair and skin conditioners, hair and skin cleansers, hair fixatives,hair dyes, hair growth promoters, deodorants, skin care compounds,permanent wave compounds, hair relaxers, hair straighteners,antibacterial compounds, antifungal compounds, anti-inflammatorycompounds, topical anesthetics, sunscreens and other cosmetic andmedicinal topically-effective compounds.

In accordance with an important feature of the present invention, thefirst topically-active compound comprises a water-soluble hairconditioner, such as a quaternary ammonium compound. Quaternary ammoniumcompounds are substantive to the hair and are excellent hairconditioners, but have a well-known incompatibility with anionicsurfactants and anionic dyes. Therefore, quaternary ammonium compoundsgenerally are not a component in shampoo-conditioner compositions oranionic dye-based compositions, but are applied to the hair from aseparate conditioning composition.

The water-soluble quaternary ammonium compounds have the generalstructural formula: ##STR1## wherein R₁ is an alkyl group including fromabout 8 to about 18 carbon atoms; R₂ is selected from the groupconsisting of an alkyl group including from about 8 to about 18 carbonatoms, a hydrogen atom, a methyl group, an ethyl group, a hydroxymethylgroup and a hydroxyethyl group; R₃ is selected from the group consistingof a benzyl group, a hydrogen atom, a methyl group, an ethyl group, ahydroxymethyl group and a hydroxyethyl group; R₄ is selected from thegroup consisting of a hydrogen atom, a methyl group, an ethyl group, ahydroxymethyl group and a hydroxyethyl group; and X is an anion. Thequaternary nitrogen of the water-soluble quaternary ammonium compoundalso can be a component of a heterocyclic nitrogen-containing moiety,such as morpholine or pyridine. The anion of the quaternary ammoniumcompound can be any common anion, such as chloride, methosulfate,ethosulfate, nitrate, bromide, tosylate, acetate, or phosphate.

The water-soluble quaternary ammonium compounds have one or two longchain alkyl groups containing from about 8 to about 18 carbon atoms. Thelong chain alkyl groups also can include, in addition to, or inreplacement of, carbon and hydrogen atoms, ether linkages or similarwater-solubilizing linkages. The remaining two or three substituents ofthe quaternary nitrogen of the quaternary ammonium compound can behydrogen; or benzyl; or short chain alkyl or hydroxyalkyl groups, suchas methyl, ethyl, hydroxymethyl or hydroxyethyl groups; or combinationsthereof, either of the same or different identity.

Exemplary water-soluble quaternary ammonium compounds include, but arenot limited to laurtrimonium chloride; Quaternium-16; lauralkoniumchloride; olealkonium chloride; dilauryldimonium chloride; cetalkoniumchloride; dicetyldimonium chloride; laurylpyridinium chloride;cetylpyridinium chloride; soyatrimonium chloride; Polyquaternium-6;Polyquaternium-7; guarhydroxypropyltrimonium chloride;Polyquaternium-11; Polyquaternium-5; Polyquaternium-10;Polyquaternium-24; cetrimonium chloride; Quaternium-24; mytrimoniumchloride; PEG-2 cocomonium chloride; PEG-2 cocoyl quaternium-4; PEG-15cocoyl quaternium-4; PEG-2 stearyl quaternium-4; PEG-15 stearylquaternium-4; PEG-2 oleyl quaternium-4; and PEG-15 oleyl quaternium-4,and mixtures thereof, wherein the compound designation is provided bythe Cosmetic, Toiletry and Fragrance Association, Inc. in the CTFACosmetic Ingredient Dictionary, 4th Ed., 1991, hereinafter referred toas the CTFA Dictionary. Other water-soluble quaternary ammoniumcompounds are listed in the CTFA Cosmetic Ingredient Handbook, 1st Ed.,1988 (hereinafter the CTFA Handbook) at pages 40-42, incorporated hereinby reference.

Other water-soluble hair conditioners also can be used as the firsttopically-active compound. Such hair conditioners include, but are notlimited to, fatty amine salts, ethoxylated fatty amine salts,dimethicone copolyols, protonated polyethylenimines, protonatedethoxylated polyethylenimines, soluble animal collagen, lauramine oxide,cationic polymers, numerous other water-soluble hair conditioners listedin the CTFA Handbook at pages 71-73, incorporated herein by reference,and mixtures thereof.

In addition to hair conditioners, a skin conditioner can be used as thefirst topically-active compound. Skin conditioning agents include, butare not limited to, humectants, such as fructose, glucose, glycerin,propylene glycol, glycereth-26, mannitol and urea; pyrrolidonecarboxylic acid; hydrolyzed lecithin; coco-betaine; cysteinehydrochloride; glutamine; PPG-15; sodium gluconate; potassium aspartate;oleyl betaine; thiamine hydrochloride; sodium laureth sulfate; sodiumhyaluronate; hydrolyzed proteins; hydrolyzed keratin; amino acids; amineoxides; water-soluble derivatives of vitamins A, E and D;amino-functional silicones; ethoxylated glycerin; alpha-hydroxy acidsand salts thereof; water-soluble fatty oil derivatives, such as PEG-24hydrogenated lanolin, almond oil, grape seed oil and castor oil;numerous other water-soluble skin conditioners listed in the CTFAHandbook, pages 79-84, incorporated herein by reference; and mixturesthereof.

The first topically-active compound also can be a hair fixative or filmformer that imparts style-retention properties to hair, i.e., sets thehair. The hair fixative typically is a homopolymer, a copolymer, or aterpolymer. The polymers can be nonionic, amphoteric, anionic orcationic. Examples of hair fixatives include, but are not limited to, anacrylamide copolymer; an acrylamide/sodium acrylate copolymer; apolystyrene sulfonate; a polyethylene oxide; a water-dispersiblepolyester; a cationic cellulose; an acrylate/ammoniummethacrylatecopolymer; an aminoethylacrylate phosphate/acrylate copolymer; apolyacrylamide; Polyquaternium-1; Polyquaternium-2; Polyquaternium-4;Polyquaternium-5; Polyquaternium-6; Polyquaternium-7; Polyquaternium-8;Polyquaternium-9; Polyquaternium-10; Polyquaternium-11;Polyquaternium-12; Polyquaternium-13; Polyquaternium-14;Polyquaternium-15; Polyquaternium-16; Polyquaternium-28; a PVP(polyvinylpyrrolidone); a PVP/dimethylaminoethylmethacrylate copolymer;a PVP/ethyl methacrylate/methacrylic acid copolymer; a carboxylatedpolyvinyl acetate; vinyl/caprolactam/PVP/dimethylaminoethyl methacrylatecopolymer (GAFFIX VC713); a PVP/vinyl acetate copolymer; a sodiumacrylate/vinyl alcohol copolymer; sodium carrageenan; a vinylacetate/crotonic acid copolymer; numerous other water-soluble hairfixatives listed in the CTFA Handbook at pages 73-74, incorporatedherein by reference; and mixtures thereof. Numerous hair fixatives alsoare disclosed in U.S. Pat. No. 5,277,899, incorporated herein byreference.

In addition, the first topically-active compound can be a water-solublehair dye, such as, but not limited to, m-aminophenol hydrochloride,p-aminophenol sulfate, 2,3-diaminophenol hydrochloride,1,5-naphthalenediol, p-phenylenediamine hydrochloride, sodium picramate,water-soluble cationic dyes, water-soluble anionic dyes, water-solubleFD&C dyes, like Blue No. 1, Blue No. 2, Red No. 3, Red No. 4, or Red No.40, water-soluble D&C dyes, like Yellow No. 10, Red No. 22 or Red No.28, and pyrogallol. Numerous other hair dyes are listed in the CTFAHandbook, pages 70-71, incorporated herein by reference.

The first topically-active compound also can be an antioxidant, likeascorbic acid or erythorbic acid; or a fluorescent whitening agent oroptical brightener, like a distyrylbiphenyl derivative, stilbene or astilbene derivative, a pyralozine derivative or a coumarin derivative.In addition, a self-tanning compound, like dihydroxy acetone, or a hairgrowth promoter, or a hair bleaching agent, like a perborate or apersulfate salt, can be the first topically-active compound.

The first topically-active compound also can be a deodorant compound,such as an astringent salt or a bioactive compound. The astringent saltsinclude organic and inorganic salts of aluminum, zirconium, zinc, andmixtures thereof. The anion of the astringent salt can be, for example,sulfate, chloride, chlorohydroxide, alum, formate, lactate, benzylsulfonate or phenyl sulfonate. Exemplary classes of antiperspirantastringent salts include aluminum halides, aluminum hydroxyhalides,zirconyl oxyhalides, zirconyl hydroxyhalides, and mixtures thereof.

Exemplary aluminum salts include aluminum chloride and the aluminumhydroxyhalides having the general formula Al₂ (OH)_(x) Q_(y).XH₂ O,wherein Q is chlorine, bromine or iodine; x is about 2 to about 5; x+yis about 6, wherein x and y are not necessarily integers; and X is about1 to about 6. Exemplary zirconium compounds include zirconium oxy saltsand zirconium hydroxy salts, also referred to as zirconyl salts andzirconyl hydroxy salts, and represented by the general empirical formulaZrO(OH)_(2-nz) L_(z), wherein z varies from about 0.9 to about 2 and isnot necessarily an integer; n is the valence of L; 2-nz is greater thanor equal to 0; and L is selected from the group consisting of halides,nitrate, sulfamate, sulfate, and mixtures thereof.

Exemplary deodorant compounds therefore include, but are not limited to,aluminum bromohydrate, potassium alum, sodium aluminum chlorohydroxylactate, aluminum sulfate, aluminum chlorohydrate, aluminum-zirconiumtetrachlorohydrate, an aluminum-zirconium polychlorohydrate complexedwith glycine, aluminum-zirconium trichlorohydrate, aluminum-zirconiumoctachlorohydrate, aluminum sesquichlorohydrate, aluminumsesquichlorohydrex PG, aluminum chlorohydrex PEG, aluminum zirconiumoctachlorohydrex glycine complex, aluminum zirconiumpentachlorohydrexglycine complex, aluminum zirconium tetrachlorohydrex glycine complex,aluminum zirconium trichlorohydrex glycine complex, aluminumchlorohydrex PG, zirconium chlorohydrate, aluminum dichlorohydrate,aluminum dichlorohydrex PEG, aluminum dichlorohydrex PG, aluminumsesquichlorohydrex PG, aluminum chloride, aluminumzirconiumpentachlorohydrate, numerous other useful antiperspirantcompounds listed in the CTFA Handbook at p. 56, incorporated herein byreference, and mixtures thereof.

In addition to the astringent salts, the deodorant compound can be abacteriostatic quaternary ammonium compound, such as, for example, cetyltrimethyl ammonium bromide, cetyl pyridinium chloride, benzethoniumchloride, diisobutylbenzoxyethoxyethyl-dimethylbenzyl ammonium chloride,sodium N-lauryl sarcosine, sodium N-polymethyl sarcosine, lauroylsarcosine, N-myristolyl glycine, potassium N-lauroyl sarcosine, andstearyl trimethyl ammonium chloride; or a bioactive compound; or acarbonate or bicarbonate salt, such as, for example, the alkali metalcarbonates and bicarbonates, and the ammonium and tetralkylammoniumcarbonates and bicarbonates.

In addition, other compounds can be included in the primary emulsion asthe first topically-active compound in an amount sufficient to performtheir intended function. For example, if the composition is intended tobe a sunscreen, then compounds such as benzophenone-4,trihydroxycinnamic acid and salts, tannic acid, uric acid, quininesalts, dihydroxy naphtholic acid; an anthranilate, diethanolaminemethoxycinnamate, p-aminobenzoic acid, phenylbenzimidazole sulfonicacid, PEG-25 p-aminobenzoic acid or triethanolamine salicylate can beincorporated into the internal aqueous W₁ phase.

Further, sunscreen compounds such as dioxybenzone, ethyl4-[bis(hydroxypropyl)] aminobenzoate, glyceryl aminobenzoate,homosalate, menthyl anthranilate, octocrylene, octyl methoxycinnamate,octyl salicylate, oxybenzone, padimate O, red petrolatum, titaniumdioxide, 4-menthylbenzylidene camphor, benzophenone-1, benzophenone-2,benzophenone-6, benzophenone-12, isopropyl dibenzoyl methane, butylmethoxydibenzoylmethane, zotocrylene, or zinc oxide can be incorporatedinto the organic phase of the primary emulsion. Other sunscreencompounds soluble in either the aqueous or organic phase are listed inCTFA Handbook, pages 86 and 87, incorporated herein by reference.

Similarly, topically-active drugs, like antifungal compounds;antibacterial compounds; anti-inflammatory compounds; topicalanesthetics; skin rash, skin disease and dermatitis medications; andanti-itch and irritation-reducing compounds can be included in thecompositions of the present invention. For example, analgesics such asbenzocaine, dyclonine hydrochloride, aloe vera and the like; anestheticssuch as butamben picrate, lidocaine hydrochloride, xylocaine and thelike; antibacterials and antiseptics, such as povidone-iodine, polymyxinb sulfate-bacitracin, zinc-neomycin sulfate-hydrocortisone,chloramphenicol, methylbenzethonium chloride, and erythromycin and thelike; antiparasitics, such as lindane; deodorants, such as chlorophyllincopper complex, aluminum chloride, aluminum chloride hexahydrate, andmethylbenzethonium chloride; essentially all dermatologicals, like acnepreparations, such as benzoyl peroxide, erythromycin-benzoyl peroxide,clindamycin phosphate, 5,7-dichloro-8-hydroxyquinoline, and the like;anti-inflammatory agents, such as alclometasone dipropionate,betamethasone valerate, and the like; burn relief ointments, such aso-amino-p-toluenesulfonamide monoacetate and the like; depigmentingagents, such as monobenzone; dermatitis relief agents, such as theactive steroid amcinonide, diflorasone diacetate, hydrocortisone, andthe like; diaper rash relief agents, such as methylbenzethonium chlorideand the like; emollients and moisturizers, such as mineral oil, PEG-4dilaurate, lanolin oil, petrolatum, mineral wax and the like;fungicides, such as butocouazole nitrate, haloprogin, clotrimazole, andthe like; herpes treatment drugs, such asO-[(2-hydroxyethoxy)-methyl]guanine; pruritic medications, such asalclometasone dipropionate, betamethasone valerate, isopropyl myristateMSD, and the like; psoriasis, seborrhea and scabicide agents, such asanthralin, methoxsalen, coal tar and the like; steroids, such as2-(acetyloxy)-9-fluoro-1',2',3',4'-tetrahydro-11-hydroxypregna-1,4-dieno[16,17-b]naphthalene-3,20-dioneand21-chloro-9-fluoro-1',2',3',4'-tetrahydro-11b-hydroxypregna-1,4-dieno[16z,17-b]naphthalene-3,20-dione.Any other medication capable of topical administration also can beincorporated in a composition of the present invention in an amountsufficient to perform its intended function. Other topically-activecompounds are listed in Remington's Pharmaceutical Sciences, 17th Ed.,Merck Publishing Co., Easton, Pa. (1985), pages 773-791 and pages1054-1058 (hereinafter Remington's), incorporated herein by reference.

An above-described first topically-active compound is designed to remainon the skin or hair to perform its intended function. However, inparticular situations, a first topically-active compound that is rinsedfrom the skin or hair can be incorporated into the internal aqueous W₁phase of the primary emulsion.

For example, a W₁ -O-W₂ multiple emulsion composition designed as apermanent wave composition can incorporate a reducing agent into theexternal aqueous phase as the second topically-active compound. Afterapplying the W₁ -O-W₂ composition to the hair and allowing thecomposition to contact the hair for a sufficient time to reduce thehair, the external aqueous phase is rinsed from the hair leavingdroplets of the primary emulsion on the hair.

The primary emulsion has incorporated therein an oxidizing agent as thefirst topically-active compound. After the oil phase, and preferably avolatile oil phase, evaporates from the primary emulsion, the oxidizingagent is released to neutralize the hair and any reducing agentremaining on the hair. Excess oxidizing agent then can be rinsed fromthe hair in a second rinsing step.

Exemplary, but non-limiting, oxidizing agents used as the firsttopically-active compound are ammonium persulfate, hydrogen peroxide,potassium bromate, potassium chromate, potassium persulfate, sodiumbromate, sodium carbonate peroxide, sodium iodate, sodium perborate,sodium persulfate, urea peroxide, and mixtures thereof. An oxidizingagent also can be the second topically-active compound when the firsttopically-active compound is a hair conditioner. In addition, the secondtopically-active compound can be a bleaching agent (i.e., an oxidizingagent) and the first topically-active compound can be a hair dye.

2. Water

Sufficient water is present in the aqueous phase such that the aqueousphase comprises about 1% to about 95% by weight of the primary emulsion.Total water present in the W₁ -O-W₂ multiple emulsion composition isabout 30% to about 99.9%, and typically about 40% to about 95%, byweight of the composition.

3. Optional Ingredients

The internal aqueous phase also can include optional ingredientstraditionally included in topically-applied compositions. These optionalingredients include, but are not limited to, dyes, fragrances,preservatives, antioxidants, detackifying agents, and similar types ofcompounds. The optional ingredients are included in the internal aqueousphase of the primary emulsion in an amount sufficient to perform theirintended function.

B. The Oil Phase

The primary W₁ /O emulsion also comprises about 0.5% to about 95%,preferably about 0.5% to about 80%, and most preferably about 0.5% toabout 75%, by weight of the primary emulsion of an oil phase;alternatively expressed as about 0.005% to about 57%, preferably about0.005% to about 48%, and most preferably about 0.005% to about 45%, byweight of the W₁ -O-W₂ multiple emulsion composition. The oil phaseencapsulates the internal aqueous W₁ phase of the primary emulsion toform droplets of about 5 to about 1,000 μ, and preferably about 10 toabout 500 μ, in diameter. The oil phase therefore provides a barrierbetween the internal aqueous phase of the primary emulsion and theexternal aqueous phase of the W₁ -O-W₂ multiple emulsion composition.The oil phase provides a sufficient barrier even though the oil phaseconstitutes as little as 0.5% by weight of the primary emulsion.

The oil phase can be a volatile oil phase, a nonvolatile oil phase, or amixture thereof. A volatile oil phase comprising a volatile siliconecompound, a volatile hydrocarbon compound, or a mixture thereof ispreferred. In the preferred embodiment, the oil phase is sufficientlyvolatile to evaporate during the process of drying the skin or hair, andthereby release the internal aqueous W₁ phase, which includes the firsttopically-active compound, to contact the skin or hair.

A nonvolatile oil phase, comprising a nonvolatile silicone compound, anonvolatile hydrocarbon compound, or a mixture thereof, remains on theskin or hair. In this embodiment, the first topically-active compound isreleased by rubbing the skin or hair to break the primary W₁ /Oemulsion.

In accordance with an important feature of the present invention, theoil phase comprises a combination of a volatile oil phase and anonvolatile oil phase. In this embodiment, an oil phase can be designedto evaporate at a preselected temperature and provide a controlledrelease of the first topically-active compound at the preselectedtemperature. Preselected temperatures are those encountered duringnormal hair drying, provided by a hair dryer, or provided by a curlingiron.

As previously stated, the oil phase also can include a water-insolubletopically-active compound in a sufficient amount to impart a particularfunctional or esthetic effect (e.g., emolliency), as long as thetopically-active compound does not adversely affect the W₁ -O-W₂multiple emulsion composition (e.g., does not impart emulsioninstability). Although the oil phase can incorporate a topically-activecompound, the topically-active compound preferably is incorporated intothe internal aqueous phase.

The oil phase can comprise a volatile oil phase, a nonvolatile oil phaseor a mixture thereof. The volatile oil phase comprises a volatilesilicone compound, a volatile hydrocarbon compound or a mixture thereof.Preferably, the volatile oil phase comprises a volatile siliconecompound. The volatile oil phase evaporates from the skin or hair torelease the first topically-active compound.

Exemplary volatile compounds include, but are not limited to, volatile,low molecular weight polydimethylsiloxane compounds. The volatile, lowmolecular weight polydimethylsiloxane compound can be either a linear ora cyclic polydimethylsiloxane compound, as long as thepolydimethylsiloxane compound has sufficient volatility to volatilizeafter topical application to the skin or hair. Preferably thepolydimethylsiloxane is a cyclic siloxane, like cyclomethicone. Thevolatile silicone evaporates relatively quickly to leave only thenonvolatile components of the primary emulsion on the skin. In general,volatile polydimethylsiloxane compounds useful in the compositions ofthe present invention include polydimethylsiloxane compounds having aviscosity of about 0.5 to about 10 cs (centistokes). The preferredvolatile polydimethylsiloxanes have a viscosity in the range of about0.5 to about 6 cs.

The cyclic, low molecular weight, volatile polydimethylsiloxanes,designated in the CTFA International Cosmetic Ingredient Dictionary, 4thEd., Cosmetic, Toiletry and Fragrance Association, Washington, DC (1991)(hereinafter CTFA Dictionary) as cyclomethicones, are the preferredsiloxanes used in a composition of the present invention. To achieve thefull advantage of the present invention, a cyclomethicone used in acomposition of the present invention is a low viscosity, low molecularweight, water-insoluble cyclic compound having an average of about 3 toabout 6 --[O-Si(CH₃)₂ ]-- repeating group units per molecule(hexamethylcyclotrisiloxane, octamethyl-cyclotetrasiloxane,decamethylcyclopentasiloxane, dodecamethylcylcohexasiloxane, andmixtures thereof); boil at atmospheric pressure at about 150° C. toabout 250° C.; and have a viscosity at 25° C. of about 2 to about 6centistokes. The polydimethyl cyclosiloxanes having an average of about4 to about 5 repeating units per molecule, i.e., the tetramet andpentamer, are especially preferred. To achieve the full advantage of thepresent invention, the volatile cyclomethicone has a boiling point atatmospheric pressure in the range of about 150° C. to about 220° C.Suitable cyclomethicones are available commercially under the tradenamesDOW CORNING 245 FLUID, DOW CORNING 344 FLUID and DOW CORNING 345 FLUIDfrom Dow Corning Corporation, Midland, Mich., and SILICONE SF-1173 andSILICONE SF-1202 from General Electric, Waterford, N.Y.

An example of a linear, low molecular weight, volatilepolydimethylsiloxane compound useful in the composition and method ofthe present invention is the compound designated in the CTFA Dictionaryas hexamethyldisiloxane, available commercially under the tradename DOWCORNING 200 FLUID from Dow Corning Corp., Midland, Mich.Hexamethyldisiloxane has a viscosity of 0.65 cs and is highly volatile.Other linear polydimethylsiloxanes, such as decamethyltetrasiloxane,having a boiling point of about 195° and a viscosity of 1.5 cs;octamethyltrisiloxane; and dodecamethylpentasiloxane, also havesufficient volatility to be useful in the composition of the presentinvention. Another useful linear siloxane is bisphenylhexamethicone. Ingeneral, it has been found that a linear, low molecular weight volatilepolydimethylsiloxane compound having a viscosity at 25° C. andatmospheric pressure of about 0.5 to about 5 cs, and a boiling point atatmospheric pressure of about 100° C. to about 250° C., is preferred foruse in the composition and method of the present invention.

The volatile oil phase also can comprise a volatile hydrocarboncompound, such as a hydrocarbon having about 10 to about 30 carbonatoms, that has sufficient volatility to slowly volatilize from the skinor hair after application of the W₁ -O-W₂ multiple emulsion compositionto the skin or hair and subsequent rinsing. A preferred volatilehydrocarbon compound is an aliphatic hydrocarbon having about 12 toabout 24 carbon atoms, and having a boiling point of about 100° C. toabout 250° C. The volatile hydrocarbon compounds perform the samefunction and provide essentially the same benefits as the volatilesilicone compounds.

Volatile hydrocarbon compounds incorporated into the primary emulsioninclude, for example, isododecane and isohexadecane, i.e,. PERMETHYL99A, PERMETHYL 101A and PERMETHYL 102A, available from Presperse, Inc.,South Plainfield, N.J. Other exemplary volatile hydrocarbon compoundsare depicted in general structural formula (I), wherein n ranges from 2to 5. ##STR2## Another exemplary volatile hydrocarbon compound is ISOPARM (a C₁₃ -C₁₄ isoparaffin available from Exxon Chemical Co., Baytown,Tex.).

As previously stated, the oil phase also can be a nonvolatile oil phase.The nonvolatile oil phase comprises a nonvolatile silicone compound, anonvolatile hydrocarbon, or a mixture thereof. Preferably, thenonvolatile oil phase comprises a nonvolatile silicone compound. Thenonvolatile oil phase does not evaporate from the skin or hair. Thefirst topically-active compound therefore is released by rubbing theskin or hair to rupture the primary W₁ /O emulsion. A nonvolatile oilphase has a boiling point at atmospheric pressure of greater than about250° C.

Exemplary nonvolatile silicone compounds include a polyalkyl siloxane, apolyaryl siloxane or a polyalkylaryl siloxane. Mixtures of thesenonvolatile silicone compounds also are useful. The nonvolatilesilicones are nonfunctional siloxanes or siloxane mixtures having aviscosity of about 10 to about 600,000 cs, and typically about 350 toabout 10,000 cs, at 25° C. The so-called "rigid silicones", as describedin U.S. Pat. No. 4,902,499, herein incorporated by reference, having aviscosity above 600,000 cs at 20° C., and a weight average molecularweight of at least about 500,000, also are useful in a composition ofthe present invention. A phenyltrimethicone also is useful as anonvolatile silicone compound.

The preferred nonvolatile silicone compound is a nonvolatilepolydimethylsiloxane compound, such as a mixture, in about a 2:1 weightratio, of a low molecular weight polydimethylsiloxane fluid and a highermolecular weight polydimethylsiloxane gum. Preferred silicone gumsinclude linear and branched polydimethylsiloxanes of the followinggeneral formula:

    (CH.sub.3).sub.3 SiO--[Si(CH.sub.3).sub.2 O].sub.n --Si(CH.sub.3).sub.3,

wherein n is a number from about 2,000 to about 15,000, and preferablyfrom about 2,000 to about 7,000. Silicone gums useful in compositions ofthe present invention are available from a variety of commercialsources, including General Electric Company, Waterford, N.Y. and DowCorning Corp., Midland, Mich.

The nonvolatile oil phase also can comprise a nonvolatile hydrocarboncompound, such as mineral oil. Other exemplary nonvolatile hydrocarboncompounds that can be incorporated into the oil phase include, but arenot limited to, a branched 1-decene oligomer, like 1-decene dimer or apolydecene.

The oil phase also optionally can comprise (1) an oil, such as jojobaoil, wheat germ oil or purcellin oil; or (2) a water-insolubleemollient, such as, for example, an ester having at least about 10carbon atoms, and preferably about 10 to about 32 carbon atoms.

Suitable esters include those comprising an aliphatic alcohol havingabout eight to about twenty carbon atoms and an aliphatic or aromaticcarboxylic acid including from two to about twelve carbon atoms, orconversely, an aliphatic alcohol having two to about twelve carbon atomswith an aliphatic or aromatic carboxylic acid including about eight toabout twenty carbon atoms. The ester is either straight-chained orbranched. Preferably, the ester has a molecular weight of less thanabout 500. Suitable esters therefore include, for example, but are notlimited to:

(a) aliphatic monohydric alcohol esters, including but not limited to:

myristyl propionate,

isopropyl isostearate,

isopropyl myristate,

isopropyl palmitate,

cetyl acetate,

cetyl propionate,

cetyl stearate,

isodecyl neopentanoate,

cetyl octanoate,

isocetyl stearate;

(b) aliphatic di- and tri-esters of polycarboxylic acids, including butnot limited to:

diisopropyl adipate,

diisostearyl fumarate,

dioctyl adipate, and

triisostearyl citrate;

(c) aliphatic polyhydric alcohol esters, including but not limited to:

propylene glycol dipelargonate;

(d) aliphatic esters of aromatic acids, including but not limited to:

C₁₂ -C₁₅ alcohol esters of benzoic acid,

octyl salicylate,

sucrose benzoate, and

dioctyl phthalate.

Numerous other esters are listed in the CTFA Handbook, at pages 24through 26, incorporated herein by reference.

C. The Surfactant Phase

The primary emulsion of the present invention also includes about 0.1%to about 20%, and preferably about 0.1% to about 15%, by weight of theprimary emulsion of a surfactant phase. To achieve the full advantage ofthe present invention, about 0.5% to about 12% by weight of thesurfactant phase is present in the primary emulsion. Alternativelyexpressed, the surfactant phase is present in an amount of about 0.001%to about 12%, preferably about 0.005% to about 7.5%, and most preferablyabout 0.05% to about 5.4%, by weight of the W₁ -O-W₂ multiple emulsioncomposition.

The surfactant phase comprises a silicon-free surfactant, or a blend ofsilicon-free surfactants, having an HLB value of about 10 or less (i.e.,an HLB value of about 0.1 to about 10), an oil-soluble silicon-basedsurfactant, an oil-soluble polymeric surfactant, or mixtures thereof.Preferably, the silicon-free surfactant or surfactant blend has an HLBvalue of about 1 to about 7. To achieve the full advantage of thepresent invention, the silicon-free surfactant or surfactant blend hasan HLB value of about 3 to about 6. The term "oil-soluble" as usedherein means a compound having a solubility of at least 0.1 g per 100 mlof oil phase to form a true solution.

The surfactant phase therefore comprises a single silicon-freesurfactant having an HLB value of about 0.1 to about 10, or a blend ofsilicon-free surfactants having different HLB values such that the blendhas an HLB value of about 1 to about 10. The surfactant phase also cancomprise a blend of an oil-soluble silicon-based surfactant, or anoil-soluble polymeric surfactant, and a silicon-free surfactant orsurfactant blend having an HLB value of about 10 or less. Theabove-described surfactant phases provide a water-in-oil emulsion.

Preferably, the surfactant phase comprises an oil-soluble silicon-basedsurfactant when the oil phase comprises a volatile or a nonvolatilesilicone compound. If the oil phase is a volatile or nonvolatilehydrocarbon compound, the surfactant phase preferably comprises asilicon-free nonionic surfactant or an oil-soluble polymeric surfactant.If a combination of a silicone compound and hydrocarbon compound is usedas the oil phase, the surfactant phase preferably comprises acombination of (1) a silicon-based surfactant and (2) an oil-solublesilicon-free surfactant, an oil-soluble polymeric surfactant or amixture thereof.

A silicon-free nonionic surfactant having an HLB value of about 0.1 toabout 10 can be used alone as the surfactant phase of the presentinvention. The surfactant phase also can comprise a blend ofsilicon-free surfactants each having an HLB value of less than 10. Inaddition, silicon-free surfactants having an HLB value of about 0.1 toabout 10 also can be used as the first surfactant of a surfactant blendhaving an HLB value of about 1 to about 10, then a silicon-freesurfactant having an HLB of greater than about 10 is the secondsurfactant of the surfactant blend having an HLB of about 1 to about 10.

Typically, silicon-free nonionic surfactants having an HLB value ofabout 10 or less have a hydrophobic moiety, such as a long chain (C₈-C₂₂) alkyl group or an alkylated aryl group, and a hydrophilic chaincomprising a small number (i.e., one to about six) of ethoxy moieties ora combination of ethoxy and propoxy moieties. The silicon-free nonionicsurfactants having an HLB of greater than about 10 typically have thesame type of hydrophobic moiety as the low HLB surfactants, but includemore ethoxy and/or propoxy moieties.

The HLB value of a particular silicon-free surfactant can be found inMcCutcheon's Emulsifiers and Detergents, North American andInternational Editions, MC Publishing Co., Glen Rock, N.J. (1993)(hereinafter McCutcheon's). Alternatively, the HLB value of a particularsurfactant can be estimated by dividing the weight percent ofoxyethylene in the surfactant by five (for surfactants including onlyethoxy moieties). In addition, the HLB value of a surfactant blend canbe estimated by the following formula:

    HLB=(wt. %A) (HLB.sub.A)+(wt. %B) (HLB.sub.B),

wherein wt. % A and wt. % B are the weight percent of surfactants A andB in the silicon-free surfactant blend, and HLB_(A) and HLB_(B) are theHLB values for surfactants A and B, respectively.

Exemplary classes of silicon-free nonionic surfactants include, but arenot limited to, polyoxyethylene ethers of fatty (C₆ -C₂₂) alcohols,polyoxyethylene/polyoxypropylene ethers of fatty (C₆ -C₂₂) alcohols,ethoxylated alkylphenols, polyethylene glycol ethers of methyl glucose,polyethylene glycol ethers of sorbitol, and mixtures thereof.

Exemplary silicon-free nonionic surfactants are the ethoxylated alcoholshaving an HLB value of about 0.1 to about 10. An especially preferredethoxylated alcohol is laureth-1, i.e., lauryl alcohol ethoxylated withan average of one mole of ethylene oxide. Other suitable ethoxylatedalcohols include laureth-2, laureth-3 and laureth-4. Numerous othernonionic surfactants having an HLB of about 0.1 to about 10 are listedin McCutcheon's at pages 229-236, incorporated herein by reference.Other exemplary silicon-free nonionic surfactants having an HLB value ofabout 0.1 to about 10 include, but are not limited to, the ethoxylatednonylphenols, ethoxylated octylphenols, ethoxylated dodecylphenols,ethoxylated fatty (C₆ -C₂₂) alcohols having four or fewer ethylene oxidemoieties, oleth-2, steareth-3, steareth-2, ceteth-2, oleth-3, andmixtures thereof.

The surfactant phase also can comprise a silicon-free surfactant blendhaving an HLB value of about 1 to about 10. The blend is a mixture of asufficient amount of a surfactant having a low HLB value, i.e., about0.1 to about 10, and a sufficient amount of a surfactant having a higherHLB value, i.e., about 1 to greater than about 10, such that thesurfactant blend has an HLB value of about 1 to about 10. Exemplary, butnonlimiting, nonionic surfactants having a high HLB value are listed inMcCutcheon's at pages 236-246, incorporated herein by reference.

Exemplary silicon-free nonionic surfactants having an HLB value greaterthan about 10 are oleth-10, octylphenol or nonylphenol ethoxylated withsix or more moles of ethylene oxide, steareth-10, trideceth-6, methylgluceth-10, dodoxynol-12, ceteth-12, C₁₁₋₁₅ pareth-20, and mixturesthereof. The identity of the high HLB surfactant is not limited as longas the resulting surfactant phase provides a stable water-in-oil primaryemulsion.

An exemplary oil-soluble silicon-based surfactant is a dimethiconecopolyol, which is a dimethylsiloxane polymer having polyoxyethyleneand/or polyoxypropylene side chains, such as DOW CORNING 3225CFORMULATION AID, available from Dow Corning Co., Midland, Mich. Thedimethicone copolyol has about 15 or fewer ethylene oxide and/orpropylene oxide monomer units, in total, in the side chains. Dimethiconecopolyols conventionally are used in conjunction with silicones becausethe oil-soluble, silicon-based surfactants are extremely soluble in avolatile or a nonvolatile silicone compound, are extremely insoluble inwater, and have a low skin irritancy potential.

Another exemplary, but nonlimiting, oil-soluble, silicon-basedsurfactant is an alkyl dimethicone copolyol, such as cetyl dimethiconecopolyol available commercially as ABIL® EM 90 from Goldschmidt ChemicalCorporation, Hopewell, Va. The alkyl dimethicone copolyols have thestructure: ##STR3## wherein p is a numeral from 7 through 17; q is anumeral from 1 through 100;

m is a numeral from 1 through 40;

n is a numeral from 0 through 200; and

PE is (C₂ H₄ O)_(a) (C₃ H₆ O)_(b) -H having a molecular weight of about250 to about 2000, wherein a and b are selected such that the weightratio of C₂ H₄ O/C₃ H₆ O is from 100/0 to 20/80.

The surfactant phase also can comprise an oil-soluble polymericsurfactant. Polymeric surfactants capable of forming water-in-oilemulsions completely cover the surface of the water droplet, are firmlyanchored at the oil-water interface, the external oil phase is a goodsolvent for the stabilizing portion of the polymeric surfactant, and thethickness of the polymer layer on the oil side of the interface issufficient to ensure stability. These surfactants can include repeatingethoxy, propoxy and/or similar alkylene oxide monomer units, e.g.,butoxy. The oil-soluble polymeric surfactants act as surfactants and arenot physically or chemically crosslinked in solution. The oil-solublepolymeric surfactants therefore are differentiated from polymericgelling agents, such as polyacrylic acid or polymethacrylic acid.

Accordingly, exemplary oil-soluble polymeric surfactants include,but-are not limited to, polyoxyethylene-polyoxypropylene blockcopolymers, and similar polyoxyalkylene block copolymers. Theoil-soluble block copolymers typically have less than about 20% byweight of ethylene oxide. Specific nonlimiting oil-soluble polymericsurfactants include Poloxamer 101, Poloxamer 105, PPG-2-Buteth-3,PPG-3-Buteth-5, PPG-5-Buteth-7, PPG-7-Buteth-10, PPG-9-Buteth-12,PPG-12-Buteth-16, PPG-15-Buteth-20, PPG-20-Buteth-30, PPG-24-Buteth-27,PPG-28-Buteth-35,and PEG-15 Butanediol. Other useful oil-solublepolymeric surfactants are poloxamines, i.e.,polyoxyethylene-polyoxypropylene block copolymers of ethylene diamine,having less than about 40% by weight ethylene oxide.

In accordance with an important feature of the present invention, thehydrophobic moiety of a silicon-free surfactant, silicon-containingsurfactant or polymeric surfactant is sufficiently soluble in the oilphase such that a sufficient amount of the surfactant is present in theoil phase to stabilize the primary W₁ /O emulsion. In one embodiment,when the oil phase comprises a silicone compound, the surfactant phasecomprises either a silicon-based surfactant, a silicon-free surfactanthaving a hydrophobic moiety preferably containing about ten to aboutfourteen carbon atoms, an oil-soluble polymeric surfactant, or a mixturethereof. If the hydrophobic moiety of the silicon-free surfactant issaturated and includes more than about 14 carbon atoms, the silicon-freesurfactant is insoluble in the silicone phase and the primary W₁ /Oemulsion is unstable. If the hydrophobic moiety includes less than about10 carbon atoms, the primary W₁ /O emulsion has a tendency to coalesce,i.e., the emulsion droplets fuse to form large droplets. The amount ofsurfactant phase necessary to provide a primary emulsion of desired W₁/O droplet diameter varies with the amount of aqueous phase in theprimary emulsion and is easily determined by those skilled in the art.

II. The External Aqueous Phase

The external aqueous phase (W₂) of the W₁ -O-W₂ multiple emulsioncomposition comprises water and an emulsifier in an amount of 0.1% toabout 15%, and preferably about 0.5% to about 10%, by weight of theexternal aqueous phase; alternatively expressed as 0.001% to about14.85%, preferably about 0.25% to about 9.9%, by weight of the W₁ -O-W₂multiple emulsion composition. To achieve the full advantage of thepresent invention, the external aqueous phase comprises about 1% toabout 8%, by weight of the external phase of an emulsifier,alternatively expressed as about 0.5% to about 7.2% by weight of themultiple emulsion composition.

The emulsifier included in the external aqueous phase has a low affinityfor the oil phase. The emulsifier therefore does not disrupt the primaryW₁ /O emulsion and avoids the formation of a simple oil-in-wateremulsion. The emulsifier is present in a sufficient amount to provide astable W₁ -O-W₂ multiple emulsion composition, wherein droplets of theprimary W₁ /O emulsion are uniformly distributed throughout the externalaqueous phase, and preferably remain uniformly distributed in theexternal aqueous phase throughout the life of the multiple emulsioncomposition. A sufficient amount of surfactant phase in the externalaqueous phase provides W₁ /O droplets of a sufficiently large size(i.e., about 0.5 to about 1000 μ) to deposit on the skin or hair, and toresist rinsing from the skin or hair.

A W₁ -O-W₂ multiple emulsion composition is tested for stabilityimmediately after the W₁ -O-W₂ multiple emulsion composition isprepared. The composition is observed under an optical microscope, andthe W₁ -O-W₂ multiple emulsion composition is defined as stable whendroplets of the primary W₁ /O emulsion are observed at a magnificationof 50. The W₁ -O-W₂ multiple emulsion composition then is examined atperiodic intervals for extended stability. Preferably, the W₁ -O-W₂multiple emulsion composition is stable for the expected product life ofthe skin or hair care product.

The emulsifier comprises a surfactant system capable of formingstabilizing liquid crystals around the W₁ /O droplets. The surfactantsystem can be a single surfactant or a blend of surfactants. In somecases, a particular surfactant cannot form a liquid crystal structurealone, but can participate in the formation of liquid crystals in thepresence of a second surfactant.

The emulsifier for the external phase does not gel the external aqueousphase, but forms a stabilizing layer of lamellar liquid crystals arounddroplets of the internal primary W₁ /O emulsion. This layer of liquidcrystals forms a barrier film that prevents coalescence between primaryemulsion droplets and precludes migration of droplet contents from theprimary emulsion to the external aqueous phase. This type of an emulsionis different from conventional emulsions which rely upon the orientationof the hydrophobic and hydrophilic components of a surfactant at anoil-water interface. The formation of a layer of lamellar liquidcrystals around the primary W₁ /O emulsion can be detected by thepresence of Maltese crosses viewed by optical microscopy through crossedpolarizing plates or by freeze fracture electron microscopy.

As previously described, the HLB value of a surfactant is an approximatemeasurement of the solubility of a surfactant in water and oil. However,an HLB value is used only when the concentration of a surfactant insolution is sufficiently low such that a molecular monolayer of thesurfactant is formed around droplets dispersed in a continuous phase,i.e., around the primary W₁ /O emulsion. At higher surfactantconcentrations, the surfactant can undergo a phase transition and theoil droplets then can be surrounded by a layer of lamellar liquidcrystals, which can improve emulsion stability. The liquid crystals arelocalized at the oil/water interface and have been observed bymicroscopy techniques.

It is theorized, but not relied upon herein, that the layer of lamellarliquid crystals provides improved multiple emulsion stability for thefollowing reasons. As primary W₁ /O emulsion droplets approach oneanother, multiple emulsion instability occurs in two steps: (1)flocculation of the W₁ /O droplets due to van der Waals forces, followedby (2) coalescence of the flocculated W₁ /O droplets. The rate ofdroplet coalescence is related to the stability of the emulsifier filmsurrounding the droplets.

Liquid crystals stabilize emulsions by affecting both steps of theinstability process. First, flocculation is reduced because the presenceof liquid crystals modifies the attractive van der Waals forces. Thepresence of liquid crystal layers around the droplets significantlyreduces interdroplet attraction. Additionally, the liquid crystalsprovide mechanical stability to the film around the primary W₁ /Odroplets, and thereby resist the film-thinning process which leads todroplet coalescence.

Exemplary classes of surfactants capable of participating in theformation of a liquid crystal structure around the primary W₁ /Oemulsion to stabilize the W₁ -O-W₂ multiple emulsion compositioninclude, but are not limited to, quaternary ammonium compounds havingtwo long alkyl chains (i.e., C₈ -C₂₂), di-long chain alkyl (C₈ -C₂₂)amines, long chain fatty (C₈ -C₂₂) alcohols, ethoxylated fatty alcohols,double-tailed anionic surfactants, and double-tailed phospholipids.Specific surfactants capable of participating in the formation of astabilizing liquid crystal structure include, but are not limited to,dicetyldimonium chloride, distearyldimonium chloride, dipalmitylamine,cetyl alcohol, stearyl alcohol, steareth-2, steareth-21, dioctylsodiumsulfosuccinate, phosphatidylserine, phosphatidylcholine and mixturesthereof.

The preferred surfactant systems capable of forming a stabilizing liquidcrystal structure are surfactant blends-that maintain the layer oflamellar liquid crystals below the Krafft temperature of thesurfactants. The Krafft temperature corresponds to the melting point ofthe hydrocarbon chains in the surfactant, and is the temperature abovewhich the surfactant hydrocarbon chains are liquid-like and disordered.Preferred liquid crystal-forming surfactants include, but are notlimited to, a mixture of cetyl alcohol, stearyl alcohol,dicetyldimmonium chloride, stearylamidopropyldimethylamine andceteareth-20; a mixture of distearyldimmonium chloride, cetrimoniumchloride, cetyl alcohol and stearyl alcohol; and a mixture of oleth-15,cetyl alcohol and stearyl alcohol.

In a preferred embodiment, the external aqueous phase comprises water,an emulsifier and a second topically-active compound. If the W₁ -O-W₂multiple emulsion composition is designed to be a hair or skin shampooor conditioner, the emulsifier present in the external aqueous phase canserve both as the emulsifier and the second topically-active compound.

The second topically-active compound is present in an amount of 0% toabout 30%, and preferably about 0.1% to about 30%, by weight of theexternal aqueous phase. Alternatively expressed, the secondtopically-active compound is present in an amount of 0% to about 30%,and preferably about 0.05% to about 30% by weight of the W₁ -O-W₂multiple emulsion composition.

The second topically-active compound typically is a water-solublecompound. The second topically-active compound can be removed from thehair or skin with the remainder of the external aqueous phase during arinsing step (e.g., a cleansing agent), or can remain on the hair afterthe rinsing step (e.g., a conditioner that is substantive to the hair).Alternatively, the W₁ -O-W₂ multiple emulsion composition is a leave-onproduct and the second topically-active compound is allowed to remain incontact with the skin or hair.

Therefore, in addition to cleansing agents, the second topically-activecompound can be a hair conditioner that is substantive to the hair, suchas a quaternary ammonium compound, and therefore is not rinsed from thehair. The second topically-active compound also can be a reducing agentused in permanent waving, such as ammonium bisulfite, ammonium sulfate,ammonium sulfite, cysteamine, ammonium thioglycolate, cysteine, cysteinehydrochloride, ethanolamine thioglycolate, hydroquinone, glycerylthioglycolate, mercaptopropionic acid, potassium metabisulfite,potassium sulfite, potassium thioglycolate, sodium bisulfite, sodiumhydrosulfite, sodium hydroxymethane sulfonate, sodium metabisulfite,sodium sulfite, sodium thioglycolate, thioglycerin, thioglycolic acid,thiolactic acid, thiosalicylic acid, or mixtures thereof. In addition, areducing agent can be the first topically-active compound, when thesecond topically-active compound is a hair cleanser.

The external aqueous phase also can include optional ingredientstraditionally included in topically-applied compositions, such asfragrances, antioxidants, detackifying agents, preservatives or dyes.

A W₁ -O-W₂ multiple emulsion composition of the present inventiontherefore can be a liquid composition having a viscosity of about 1 toabout 15,000 cps, as measured on a Brookfield Viscometer using a #4spindle at a speed of 20 rpm. For a hair care composition, thecomposition preferably has a viscosity of about 100 to about 10,000 cps.To achieve the full advantage of the present invention, the W₁ -O-W₂multiple emulsion composition has a viscosity of about 1,000 to about9,000 cps.

The W₁ -O-W₂ multiple emulsion also can be a cream-like compositionhaving a viscosity of about 50,000 to about 1,200,000 cps, as measuredon a Brookfield Viscometer using a T-BAR spindle at a speed of 2.5 rpm.The relatively high viscosity can be achieved by the addition of agelling agent, preferably a nonpolymeric gelling agent, or can arise dueto the identity and amount of ingredients in the W₁ -O-W₂ multipleemulsion composition.

The W₁ -O-W₂ multiple emulsion compositions typically are prepared by atwo-step process. In the two-step process, the primary water-in-oil (W₁/O) emulsion is manufactured first, then is dispersed in the externalaqueous phase (W₂). The second step of the two-step process emulsifiesthe primary W₁ /O emulsion. This two-step manufacturing method allowsfor the preparation of an internal aqueous phase (W₁) different incomposition from the external aqueous phase (W₂).

In the manufacture of the primary W₁ /O emulsion, the surfactant phaseis admixed with the oil phase, then the aqueous phase is dispersed inthe combined surfactant and oil phases under high shear conditions andpreferably in a homogenizer (e.g., about 17,000 rpm in an IKAHomogenizer, available from IKA Laboratories, Cincinnati, Ohio). Primaryemulsions that were homogenized provided smaller particle size dropletsof the internal aqueous phase (W₁) (i.e., about 1 μ to about 75 μ indiameter), which were more uniform in size. Primary emulsions that werehomogenized therefore had increased stability.

The resulting primary W₁ /O emulsion then is dispersed in the externalaqueous phase (W₂) using low shear mixing (e.g., about 130 rpm on abench scale mixer). Intensive, high shear mixing during thismanufacturing step has a tendency to destroy the primary emulsion andrelease the contents of the internal W₁ aqueous phase.

The two-step manufacturing method also allows a formulator to preparedifferent primary W₁ /O emulsions, i.e., primary emulsions thatincorporate different topically-active compounds into the internalaqueous phase. Then, the W₁ /O primary emulsions each can be convertedinto a W₁ -O-W₂ multiple emulsion composition having an external aqueousphase (W₂) of the same composition. The two W₁ -O-W₂ compositions thencan be admixed to provide a multiple emulsion composition incorporatingdifferent primary W₁ /O emulsions having different topically-activecompounds which perform different or complementary functions.

The following examples are illustrative of the primary W₁ /O emulsionsand the W₁ -O-W₂ multiple emulsion compositions of the presentinvention. However, the present invention is not limited to the specificexamples set forth below. In the following examples, all amounts of thevarious ingredients are expressed by weight percentages unless otherwisespecified.

As demonstrated in the following examples, the W₁ -O-W₂ multipleemulsion compositions of the present invention were phase-stable for atleast a sufficient time to detect the W₁ -O-W₂ multiple emulsion by anoptical microscope. It is within the skill of persons in the art tooptimize the identity of composition ingredients and weight percentagesto provide W₁ -O-W₂ multiple emulsion compositions that are phase-stableover the expected life of the composition. The W₁ -O-W₂ multipleemulsion compositions also were moderately viscous liquids to creams;were easy to apply; and effectively delivered the topically-activecompounds to the skin or hair. Each of the following examples wasprepared by the above-described two-step method.

The following Examples 1-29 illustrate W₁ -O-W₂ multiple emulsioncompositions wherein the first topically-active compound in the internalW₁ aqueous phase is a hair fixative resin and the secondtopically-active compound in the external W₂ aqueous phase is a cationichair conditioner or an anionic hair cleanser. The cationic surfactantsystems present in the external aqueous phase (W₂) of Examples 1-29 forma layer of lamellar liquid crystals around the primary W₁ /O emulsion tostabilize the W₁ -O-W₂ multiple emulsion compositions.

In addition to Examples 1-29, numerous other combinations of first andsecond topically-active compounds are envisioned. For example, if thesecond topically-active compound is a conditioner, the firsttopically-active compound can be a true bodifier (e.g., a styling aidresin), a curling iron-activated styling aid, a protein (e.g.,hydrogenated wheat protein or hydrolyzed keratin protein), a sunscreen,an optical brightener (e.g., 2-pyrrolidone-5-carboxylic acid), ahumectant, or a water-soluble or water-dispersible hair dye.

If the second topically-active ingredient is a skin cleanser, the firsttopically-active ingredient can be a skin care product for dry skin(e.g., glycerin, propylene glycol, sorbitol, proline, urea, hyaluronateof dimethylsilanol, allantoin, aloe vera, pyrrolidone carboxylic acid orhydrolyzing collagen) or for oily skin (e.g., provitamin B₅).

In accordance with an important feature of the present invention,incompatible compounds can be incorporated as the first and secondtopically-active compounds because the incompatible compounds do notcome in contact in the W₁ -O-W₂ multiple emulsion composition. Forexample, if the second topically-active compound is a cleanser (e.g., ananionic surfactant), the first topically-active compound can be a hairconditioner (e.g., a cationic surfactant), a hair fixative, a sunscreen,an optical brightener, a hair dye, a deodorant, a skin care product, ahumectant, or a bacteriocide or other topical medicament.

Exemplary, but non-limiting, combinations of first and secondtopically-active compounds in a W₁ -O-W₂ multiple emulsion compositionof the present invention are:

    ______________________________________                                        First Topically-Active Compound                                                                Second Topically-Active Compound                             ______________________________________                                        Neutralizer for reducing agents                                                                Reducing agent for permanent wave                            Reducing Agent for                                                                             Hair Cleanser                                                Permanent Wave                                                                Reducing Agent for                                                                             Hair Conditioner                                             Permanent Wave                                                                Neutralizer      Cysteamine                                                   Neutralizer      Hair Conditioner                                             Hair Conditioner Neutralizer                                                  Hair Fixative Resin                                                                            Hair Fixative Resin (incompatible)                           Topical Medicament                                                                             Topical Anesthetic                                           Sun Conditioner  Make-up Remover                                              Sunburn Reliever (e.g., vitamin F)                                                             Skin Cleanser                                                Sunscreen        Skin Cleanser                                                Skin Conditioner Skin Cleanser                                                Bacteriocide     Skin Cleanser                                                Deodorant        Skin Cleanser                                                Antifungal Compound                                                                            Skin Cleanser                                                Anesthetic       Skin Cleanser                                                Anti-Inflammtory Skin Cleanser                                                Anti-Irritant    Skin Cleanser                                                Medicament       Skin Cleanser                                                Anti-Itch Compound                                                                             Skin Cleanser                                                Self-Tanning Compound                                                                          Skin Cleanser                                                Self-Tanning Compound                                                                          Skin Conditioner                                             Dermatitis Medication                                                                          Skin Cleanser                                                Hair Conditioner Hair Cleanser                                                Hair Fixative    Hair Cleanser                                                Hair Dye         Hair Cleanser                                                Hair Dye         Hair Conditioner                                             Hair Dye         Bleaching Agent                                              Sunscreen        Hair Conditioner                                             Protein          Hair Conditioner                                             Humectant        Hair Conditioner                                             Hair Growth Promoter                                                                           Hair Cleanser                                                Hair Bleaching Agent                                                                           Hair Cleanser                                                Water-Soluble Hair Conditioner                                                                 Substantive Hair Conditioner                                 ______________________________________                                    

EXAMPLES 1-29

Examples 1-29 were prepared in an essentially identical manner by thetwo-step process. The primary W₁ /O emulsion first was prepared asdescribed above. The primary emulsion of each example had a ratio ofaqueous phase/oil phase/surfactant phase (W/O/S) summarized in Table 1.The aqueous phase W₁ /O incorporated about 20% to about 40% by weight ofthe primary emulsion of a hair fixative resin, such aspolyvinylpyrrolidone or the quaternized copolymer of vinylpyrrolidoneand dimethylaminoethyl methacrylate, as summarized in Table 1. Thesurfactant phase was either cetyl dimethicone copolyol or dimethiconecopolyol. The oil phase was a volatile silicone compound, i.e.,cyclomethicone. It was found that primary emulsions containing about 60%by weight aqueous phase W₁ had excellent stability.

In Examples 1-28, the external aqueous phase (W₂) was Hair ConditionerBase No. 1 having the following formula:

    ______________________________________                                        Hair Conditioner Base No. 1                                                   (External Aqueous Phase)                                                      Ingredient               Weight %.sup.5)                                      ______________________________________                                        Soft water               q.s. to 100                                          Citric acid (50% aqueous)                                                                              0.185                                                Stearamidopropyldimethylamine.sup.1)                                                                   0.5                                                  Propylene glycol         0.5                                                  Dicetyldimonium chloride/PG.sup.2)                                                                     2.1                                                  Stearyl alcohol and Ceteareth-20 Blend.sup.3)                                                          1.0                                                  Cetyl alcohol            3.25                                                 Potassium chloride       0.1                                                  Disodium EDTA            0.1                                                  Methylchloroisothiazoline/                                                                             0.05                                                 methylisothiazolinone.sup.4)                                                  DMDM hydantoin.sup.4)    0.1                                                  Potassium hydroxide (50% aqueous)                                                                      0.033                                                Fragrance                0.2                                                  ______________________________________                                         .sup.1) LEXAMINE S13, available as a 100% active material, from Inolex        Chemical Co., Philadelphia, PA;                                               .sup.2) VARISOFT 432PG, available as a 68% active material, from Sherex       Chemical Co., Dublin, OH, to provide 1.43% active material in the final       formulation;                                                                  .sup.3) PROMULGEN G, available as a 100% active blend, from Amerchol          Corp., Edison, NJ;                                                            .sup.4) preservatives; and                                                    .sup.5) based on the weight raw material added to the hair conditioner        base.                                                                    

In Example 29, the external aqueous phase was Hair Conditioner Base No.2 having the following formula:

    ______________________________________                                        Hair Conditioner Base No. 2                                                   (External Aqueous Phase)                                                      Ingredient             Wt. %.sup.5)                                           ______________________________________                                        Soft water             q.s. to 100                                            Citric acid (50% aqueous)                                                                            0.02                                                   Hydroxyethylcellulose  0.3                                                    Distearyldimonium chloride.sup.6)                                                                    1.1                                                    Cetrimonium chloride.sup.7)                                                                          1.2                                                    Cetyl/stearyl alcohol.sup.8)                                                                         1.9                                                    Dyes                   0.0008                                                 Potassium chloride     0.3                                                    Disodium EDTA          0.01                                                   Methylchloroisothiazoline/                                                                           0.05                                                   methylisothiazolinone.sup.4)                                                  DMDM hydantoin.sup.4)  0.2                                                    Fragrance              0.2                                                    ______________________________________                                         .sup.6) AROSURF ® TA100, available as a 100% active material, from        Witco Corp., NY, NY;                                                          .sup.7) BARQUAT CT29, available as a 30% active material, from Lonza Inc.     Fairlawn, NJ, to provide 0.57% active material in the final formulation;      and                                                                           .sup.8) available as a 100% active material, from Witco Corp., NY, NY.   

The primary W₁ /O emulsion was added to the external phase, withmoderate stirring, in an amount of 4.5% to 55% by weight, based on thefinal weight of the W₁ -O-W₂ multiple emulsion composition.

In particular, the W₁ -O-W₂ multiple emulsion compositions of Examples1-28 were manufactured as follows. Hair Conditioner Base No. 1 wasprepared by heating the soft water (i.e., tap water softened by passagethrough an ion exchange column) to about 155° to 160° F., then addingthe citric acid, stearamidopropyl-dimethylamine, and propylene glycol tothe heated water. Next, the dicetyldimonium chloride/PG was added, andthe resulting mixture was stirred for 5 minutes. When the mixture washomogeneous, the stearyl alcohol/ceteareth-20 blend was added to themixture at a temperature above 145° F. The cetyl alcohol was added next,and the resulting mixture was stirred at high speed (i.e., about 130 rpmon a production scale mixer). After all the ingredients were dispersed,mixing was continued for 30 minutes at 155° F. Then, the mixture wascooled to 130°-135° F., followed by the addition of potassium hydroxide(diluted 1:8 with soft water). In a separate container, the potassiumchloride and disodium EDTA were completely dissolved in 120° F. softwater, then, at 117°-122° F., the salt solution was slowly added to thebatch mixture. After cooling the resulting mixture, i.e., HairConditioner Base No. 1, to 110° F. or less, the primary W₁ /O emulsion,preservatives and fragrance were added to the mixture. The resulting W₁-O-W₂ multiple emulsion composition was cooled to 100°-105° F., and lowshear mixing was continued for about 30 minutes. Finally, the pH wasadjusted to about 4.5 to about 6.1 with liquid citric acid or potassiumhydroxide. Alternatively, the primary W₁ /O emulsion can be incorporatedinto the mixture after pH adjustment. The composition of Example 29 wasprepared in a similar two-step method.

The following Table I illustrates Examples 1-29 wherein differentparameters with respect to the primary W₁ /O emulsion and the externalaqueous phase (W₂) were varied. Examples 1 and 2 are control examples inwhich cyclomethicone was incorporated directly into the hair conditionerbase. The presence of a W₁ -O-W₂ multiple emulsion was confirmed byoptical microscopy.

                                      TABLE I                                     __________________________________________________________________________                     SUR-                                                         EX-  %           FAC-                                                         AMPLE                                                                              SILICONE.sup.9)                                                                     W/O/S.sup.10)                                                                       TANT.sup.11)                                                                        RESIN.sup.14)  REMARKS                                 __________________________________________________________________________    1    1.8   --    --    --             Hair Conditioner Base No. 1                                                   (control)                               (compara-                                                                     tive)                                                                         2    3.0   --    --    --             Hair Conditioner Base No. 1 with                                              more cyclomethicone                     (compara-                             (control)                               tive)                                                                         3    1.8   46/46/8                                                                             Cetyl --             Multiple emulsion observed under a                                            light microscope                                         Dimethicone                                                                   Copolyol.sup.12)                                             4    1.8   60/30/10H.sup.17)                                                                   Cetyl Polyvinylpyrrolidone.sup.15) (1.1%)                                                          Curl retention (quantitative) was                                             noted on hair tresses,                                   Dimethicone          resin coating felt on hair                               Copolyol.sup.12)                                             5    3.0   60/30/10H                                                                           Cetyl Polyvinylpyrrolidone.sup.15) (1.8%)                                                          Resin coating felt on hair, stable                                            for 3 months.sup.18) ; weak                              Dimethicone          set retention of tresses.sup.19)                         Copolyol.sup.12)                                             6    4.0   60/30/10H                                                                           Cetyl Polyvinylpyrrolidone.sup.15) (2.4%)                                                          Identical set retention                                                       (qualitative) as Example 5                               Dimethicone                                                                   Copolyol.sup.12)                                             7    3.0   --    Cetyl Polyvinylpyrrolidone.sup.15)                                                                 Components added separately, no                                               primary emulsion                        (compara-        Dimethicone          formed;                                 tive)            Copolyol.sup.12)                                             8    4.5   60/30/10H                                                                           Cetyl Polyvinylpyrrolidone.sup.15) (2.7%)                                                          Tress curl retention improved over                                            Example 5                                                Dimethicone                                                                   Copolyol.sup.12)                                             9    3.0   50/40/10                                                                            Cetyl Quaternized copolymer of                                                                     Set retention greater than                                                    polyvinylpyrrolidone                                     Dimethicone                                                                         vinylpyrrolidone and                                                                         (qualititive) of Example 5; stable                                            for 3 months                                             Copolyol.sup.12)                                                                    dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (0.75%)                    10   4.0   50/40/10                                                                            Cetyl Quaternized copolymer of                                                                     Slightly better set retention than                                            Example 9                                                Dimethicone                                                                         vinylpyrrolidone and                                                                         (qualitative); stable for 3 months                       Copolyol.sup.12)                                                                    dimethylaminoethyl methacrylate                                               (Polyquaternium 11.sup.16) (0.90%)                     11   3.0   70/20/10UH                                                                          Cetyl Quaternized copolymer of                                                                     Salon test.sup.20) : wetcomb poorer                                           than control (Example 1)                                 Dimethicone                                                                         vinylpyrrolidone and                                                                         hold and set retention identical to                                           control                                                  Copolyol.sup.12)                                                                    dimethylaminoethyl methacrylate                                                              performance: curl retention                                                   significantly better than                                      (Polyquaternium 11).sup.16) (2.1%)                                                           control; stable for 3 months            12   3.0   70/20/10H                                                                           Cetyl Quaternized copolymer of                                                                     Salon test: wetcomb poorer than                                               control                                                  Dimethicone                                                                         vinylpyrrolidone and                                                                         hold and set retention greater than                                           control                                                  Copolyol.sup.12)                                                                    dimethylaminoethyl methacrylate                                                              performance: curl retention                                                   significatnly better than                                      (Polyquaternium 11).sup.16) (2.1%)                                                           Example 11; stable for 3 months         13   3.0   70/20/10                                                                            Cetyl Quaternized copolymer of                                                                     Components added separately             (compara-        Dimethicone                                                                         vinylpyrrolidone and                                                                         sensory performance poorer than                                               Example 14                              tive)            Copolyol.sup.12)                                                                    dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (2.1%)                     14   3.0   70/20/10H                                                                           Cetyl Quaternized copolymer of                                                                     Sensory performance greater than                                              Example 13                                               Dimethicone                                                                         vinylpyrrolidone and                                                    Copolyol.sup.12)                                                                    dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (2.1%)                     15   3.0   80/17/3                                                                             Dimethicone                                                                         Quaternized copolymer of                                                                     Components added separately             (compara-        copolyol.sup.13)                                                                    vinylpyrrolidone and                                                                         salon: observed poorer performance                                            compared to                             tive)                  dimethylaminoethyl methacrylate                                                              Ex. 16                                                         (Polyquaternium 11).sup.16) (2.8%)                     16   3.0   80/17/3H                                                                            Dimethicone                                                                         Quaternized copolymer of                                                                     Salont test: no difference in                                                 hold/curl retention compared                             copolyol.sup.13)                                                                    vinylpyrrolidone and                                                                         to Ex. 9, stable for about 2                                                  months                                                         dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (2.8%)                     17   1.8   80/17/3                                                                             Dimethicone                                                                         Quaternized copolymer of                                                                     Components added separately             (compara-        copolyol.sup.13)                                                                    vinylpyrrolidone and                                   tive)                  dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (1.7%)                     18   1.8   80/17/3H                                                                            Dimethicone                                                                         Quaternized copolymer of                                                                     Added as emulsion, significant                                                increase in composition                                  copolyol.sup.13)                                                                    vinylpyrrolidone and                                                                         viscosity compared to Example 17                               dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (1.7%)                     19   1.8   85/10/5                                                                             Dimethicone                                                                         Quaternized copolymer of                                                                     Components added separately             (compara-        copolyol.sup.13)                                                                    vinylpyrrolidone and                                   tive)                  dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (3.1%)                     20   1.8   85/10/5H                                                                            Dimethicone                                                                         Quaternized copolymer of                                                                     Viscosity 6000 cps, salon study 4                                             of 6 models had                                          copolyol.sup.13)                                                                    vinylpyrrolidone and                                                                         worse curl retention than identical                                           composition using                                              dimethylaminoethyl methacrylate                                                              cetyl dimethicone copolyol (Example                                           13), stability about                                           (Polyquaternium 11).sup.16) (3.1%)                                                           45 days                                 21   1.8   85/10/5H                                                                            Cetyl Quaternized copolymer of                                                                     Viscosity 1080 cps, stability                                                 greater than 45 days                                     Dimethicone                                                                         vinylpyrrolidone and                                                    Copolyol.sup.12)                                                                    dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (3.1%)                     22   3.0   85/10/5H                                                                            Dimethicone                                                                         Quaternized coppolymer of                                                                    Salon study: worse combing but                                                better curl than control                                 Copolyol.sup.13)                                                                    vinylpyrrolidone and                                                                         Example 1; stability greater than                                             one month                                                      dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (5.1%)                     23   3.0   85/10/5H                                                                            Cetyl Quaternized copolymer of                                                                     Salon study: worse combing, but                                               better curl retention                                    Dimethicone                                                                         vinylpyrrolidone and                                                                         after 4 to 5 hours; stability                                                 greater than one month                                   Copolyol.sup.12)                                                                    dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (5.1%)                     24   5.0   85/10/5H                                                                            Cetyl Quaternized copolymer of                                                                     Stability greater than 12 days                           Dimethicone                                                                         vinylpyrrolidone and                                                    Copolyol.sup.12)                                                                    dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (8.5%)                     25   5.5   85/10/5H                                                                            Cetyl Quaternized copolymer of                                                                     Stability greater than 2 days                            Dimethicone                                                                         vinylpyrrolidone and                                                    Copolyol.sup.12)                                                                    dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (9.35%)                    26   1.8   87/10/3H                                                                            Dimethicone                                                                         Quaternized copolymer of                                                                     Stability about 45 days                                  Copolyol.sup.13)                                                                    vinylpyrrolidone and                                                          dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (3.1%)                     27   3.0   70/20/10H                                                                           Cetyl Vinylpyrrolidone/methacrylamido-                                                             Stability greater than 7 days                            Dimethicone                                                                         propyltrimethylammonium                                                 Copolyol.sup.12)                                                                    chloride copolymer                                                            (Polyquaternium 28).sup.21) (2.1%)                     28   3.0   70/20/10H                                                                           Cetyl PVP/Dimethylaminoethyl-                                                                      Stability greater than 7 days                            Dimethicone                                                                         methacrylate Copolymer.sup.22) (2.1%)                                   Copolyol.sup.12)                                             29.sup.23)                                                                         3.0   85/10/5H                                                                            Cetyl Quaternized copolymer of                                                                     Treated tresses exhibited extra                                               body in salon tests,                                     Dimethicone                                                                         vinylpyrrolidone and                                                                         stability greater than 5 days                            Copolyol.sup.12)                                                                    dimethylaminoethyl methacrylate                                               (Polyquaternium 11).sup.16) (5.1%)                     __________________________________________________________________________     .sup.9) % volatile silicone (cycolmethicone) in the final W.sub.1             --O--W.sub.2 multiple emulsion composition or contol;                         .sup.10) weight ratio of water phase (W) to volatile oil phase (O) to         surfactant phase (S) in the primary W.sub.1 /O emulsion;                      .sup.11) surfactant present in the surfactant phase of the primary            W.sub.1/ O emulsion;                                                          .sup.12) ABIL ® EM90, available as a 100% active compound from            Goldschmidt Chemical Corporation, Hopewell, VA;                               .sup.13) SILWET Surfactant L7622, available as a 100% active compound fro     OSi Specialties, Inc., Tarrytown, NY;                                         .sup.14) Hair fixative resin present in the primary W.sub.1 /O emulsion a     the first topicallyactive compound, and the % by weight of the hair           fixative resin in the W.sub.1 --O--W.sub.2 multiple emulsion composition;     .sup.15) PVP K30 (M.W. 38,000), available from ISP Corp., Wayne, NJ, and      added as a 30% aqueous solution;                                              .sup.16) GAFQUAT 755N (M.W. 1,000,000), available from ISP Corp., Wayne,      NJ, as a 20% aqueous solution;                                                .sup.17) H: homogenized, UH: unhomogenized;                                   .sup.18) sample stability tested at room temperature;                         .sup.19) comparison to control sample of Example 1 unless otherwise noted     .sup.20) salon tests were performed on six models;                            .sup.21) GAFQUAT HS100 (M.W. 1,000,000), available from ISP Chemcials         Inc., Wayne, NJ, as a 20% aqueous solution;                                   .sup.22) COPOLYMER 845 (M.W. 1,000,000), available from ISP Chemcials         Inc., Wayne, NJ, as a 20% aqueous solution; and                               .sup.23) the external aqueous phase was the cationic surfactantbased Hair     Conditioner Base No. 2.                                                  

Various compositions summarized in Table I were applied to virgin brownhair tresses, available from DeMeo Bros., NY, N.Y. The compositions wereworked into the hair, then rinsed from the hair. The hair tresses thenwere dried. The hair tresses were examined visually. Salon tests on sixhuman models also were conducted. The technicians empirically rated hairtreated with the W₁ -O-W₂ multiple emulsion compositions, and theresults were averaged.

As shown in Table I, the W₁ -O-W₂ multiple emulsion compositionsoutperformed the comparative compositions of Examples 1, 2, 7, 13, 15,17 and 19, wherein the ingredients were added separately as opposed tofirst forming a primary W₁ /O emulsion.

In particular, mass spectrometry indicated that cyclomethicone remainedon the hair after rinsing, i.e., the primary emulsion was deposited.After drying the hair, the resin was released to impart set retentionproperties to the hair.

In addition, it was observed that resin was deposited on the hair. Hairtreated with the compositions of Examples 11 and 12 had detectableamounts of resin deposited on the hair shaft. This was confirmed byscanning electron micrographs of hair treated with the compositions ofExamples 11 and 12, compared to hair treated with a control sample(Example 2) that did not include a resin and compared to rinsed andunrinsed hair samples treated with an aqueous resin solution (0.5% byweight GAFQUAT 755N). The composition of Example 12, which washomogenized, applied a more uniform and thinner coating of resin on thehair, which is preferred.

Table I also illustrates that the W₁ -O-W₂ multiple emulsioncompositions of the present invention exhibit a stability of greaterthan 3 months (Examples 5 and 9-12) and that 55% by weight of a primaryW₁ /O emulsion can be incorporated into the W₁ -O-W₂ multiple emulsioncomposition (Example 25).

In addition to the compositions of Examples 1-29, other W₁ -O-W₂multiple emulsion compositions were prepared which incorporated a firsttopically-active ingredient different from a hair styling resin. TheseW₁ -O-W₂ compositions are illustrated in Table II as Examples 30-35. Thecompositions of Examples 30-35 incorporated either a water-soluble dye,a sunscreen, an optical brightener or a permanent wave composition asthe first topically-active compound in the primary W₁ /O emulsion. Thecompositions of Examples 30-35 were prepared by the two-step method setforth above with respect to Examples 1-29.

                                      TABLE II                                    __________________________________________________________________________    EX-  %                    FIRST TOPICALLY-                                                                         EXTERNAL                                 AMPLE                                                                              SILICONE.sup.9)                                                                     W/O/S.sup.10)                                                                       SURFACTANT.sup.11)                                                                     ACTIVE COMPOUND                                                                          PHASE   REMARKS                          __________________________________________________________________________    30   1.87  72/18.7/9.3                                                                         Cetyl Dimethicone                                                                      FD&C Red No. 22                                                                          Hair Condition                                                                        The composition was applied                                                   to virgin                                         Copolyol.sup.12)                                                                       (dye) 10%.sup.25)                                                                        Base No. 1                                                                            white tresses of hair. The                                                    composition                                                                   of Example 31 dyed the                                                        tresses. No dye                                                               deposition observed with a                                                    control oil-in-                                                               water composition; stability                                                  at least one                                                                  day.sup.18)                      31   1.87  72/18.7/9.3                                                                         Cetyl Dimethicone                                                                      Tri-K Arianor Madden                                                                     Hair Conditioner                                                                      Stability greater than 6                                                      days at room                                      Copolyol.sup.12)                                                                       Red (dye) 1%.sup.25)                                                                     Base No. 1                                                                            temperature and at                                                            100° F., up to 6                                                       days                                                                          at 120° F.                32   1.87  72/18.7/9.3                                                                         Cetyl Dimethicone                                                                      Tri-K Arianor Madden                                                                     Hair Conditioner                                                                      Individual W.sub.1 droplets                                                   including either                                  Copolyol.sup.12)                                                                       Red (dye) 1% and                                                                         Base No. 1                                                                            blue or red dye were                                                          observed under an                                          Tri-K Arianor Steel                                                                              optical microscope                                         Blue (dye) 1%.sup.25)                               33   3.44  74/20.7/5.3                                                                         Cetyl Dimethicone                                                                      Benzophenone-4                                                                           Hair Conditioner                                                                      The presence of suncsreen on                                                  treated                                           Copolyol.sup.12)                                                                       (sunscreen) 5%.sup.25)                                                                   Base No. 1                                                                            hair was detected by                                                          UV/visible light                                                              absorption; gas                                                               chromatography/mass                                                           spectroscopy detected about                                                   10 ppm of                                                                     sunscreen per gram of hair;                                                   stability                                                                     greater than one week            34   2.76  77.7/13.8/8.5                                                                       Cetyl Dimethicone                                                                      Stilbene Derivative.sup.26)                                                              Hair Conditioner                                                                      Stability at least one week                       Copolyol.sup.12)                                                                       (optical brightener)                                                                     Base No. 1                                                         10%.sup.25)                                         35   3.0   70/20/10                                                                            Cetyl Dimethicone                                                                      Hair Reducing Base                                                                       Hair Conditioner                                                                      Stability greater than 3                                                      weeks                                             Copolyol.sup.12)                                                                       No. 1.sup.27)                                                                            Base No. 1                                                         (5.75% cysteamine HCl                                                         0.5% ammonium                                                                 hydroxide                                                                     1.4% ammonium                                                                 chloride)                                           __________________________________________________________________________    .sup.24) ABIL ® Wax 2434, available as a 100% active compound from        Goldschmidt Chemical Corp., Hopewell, VA;                                     .sup.25) wt. % of first topically-active material in W.sub.1 ;                .sup.26) LEUCOPHOR BSB, available as a 100% active compound from Sandoz       Chemicals Corp., Charlotte, NC; and                                           .sup.27) Hair Reducing Base No 1 includes:                                        water         84.5 (wt %)                                                     cysteamine HCl (75%)                                                                        11.0                                                            ammonium hydroxide (28%)                                                                    2.5                                                             ammonium bicarbonate                                                                        2.0.                                                    

The compositions of Examples 30 and 33 demonstrate W₁ -O-W₂ multipleemulsion compositions of the present invention that incorporateincompatible first and second topically-active compounds. In Example 30,the first topically-active compound is an anionic dye and the secondtopically-active compound is a cationic quaternary ammonium compound.Simply admixing aqueous solutions of the anionic dye and cationicquaternary ammonium compound resulted in an immediate precipitate.However, adding the primary W₁ /O emulsion incorporating the anionic dyeto the external aqueous phase (W₂) incorporating the cationic saltprovided a homogeneous composition, without the formation of aprecipitate. The primary W₁ /O emulsion prevents formation of aprecipitate because the oil phase separates the incompatibletopically-active ingredients. The W₁ -O-W₂ multiple emulsion compositionof Examples 30 and 33 were stabilized by a layer of lamellar liquidcrystals that formed around the primary W₁ /O emulsion droplets.

The composition of Example 30 also effectively dyed virgin white tressesof hair. White hair tresses were not dyed by a composition wherein theanionic dye was simply admixed with the cationic quaternary ammoniumcompound. In this composition, the dye was not available to treat thehair because the dye interacted with the cationic quaternary ammoniumcompound.

Similarly, Example 33 incorporates an anionic sunscreen agent and acationic quaternary ammonium salt. If benzophenone-4 is added directlyto Hair Conditioner Base No. 1, a precipitate results. However, adding aprimary W₁ /O emulsion incorporating benzophenone-4 into the internal W₁phase prevented formation of a precipitate. The multiple emulsioncomposition of Example 33 was stabilized by the formation of a layer oflamellar liquid crystals around the primary W₁ /O emulsion droplets.

The following Table III illustrates other primary W₁ /O emulsions thathave been prepared, then incorporated into Hair Conditioner Base No. 1to provide a W₁ -O-W₂ multiple emulsion composition of the presentinvention. Hair Conditioner Base No. 1 is a cationic composition capableof emulsifying silicone oils and destroying the primary emulsion.However, the primary W₁ /O emulsions were stable when emulsified intothe cationic hair conditioner base under low shear conditions. HairConditioner Base No. 1 includes a di-long chain alkyl quaternaryammonium compound that acts as an emulsifier and participates in forminga stabilizing layer of lamellar liquid crystals around the primary W₁ /Oemulsion droplets. Examples 1-89 also provided evidence that thewater-soluble, first topically-active compound present in the internalaqueous phase remains on the hair in sufficient quantity to perform itsintended function.

                                      TABLE III                                   __________________________________________________________________________                                     INTERNAL                                                  %                   AQUEOUS                                      EXAMPLE                                                                             W/O/S.sup.10)                                                                        SILICONE.sup.28)                                                                      SURFACTANT.sup.11)                                                                        PHASE.sup.30)                                __________________________________________________________________________    36    70/20/10                                                                             20      Cetyl Dimethicone                                                                         PVP/Dimethylaminoethyl-                                           Copolyol.sup.12)                                                                          methacrylate Copolymer.sup.22)               37    70/20/10                                                                             20      Cetyl Dimethicone                                                                         Sodium Polystyrene Sulfonate.sup.29)                              Copolyol.sup.12)                                         38    85/10/5                                                                              10      Dimethicone Copolyol.sup.13)                                                              Polyquaternium 11.sup.16)                                         (60%) and Laureth-4                                                           (40%)                                                    39    85/10/5                                                                              10      Dimethicone Copolyol                                                                      Polyquaternium 11.sup.16)                                         (60%) and Laureth-1                                                           (40%)                                                    40    70/20/10                                                                             20      Cetyl Dimethicone                                                                         Polyquaternium 28.sup.21)                                         Copolyol.sup.12)                                         41    60/30/10                                                                             30      Cetyl Dimethicone                                                                         Polyvinylpyrrolidone.sup.15)                                      Copolyol.sup.12)                                         42    70/20/10                                                                             20      Cetyl Dimethicone                                                                         Polyvinylmethacrylate methyl                                      Copolyol.sup.12)                                                                          acrylate decadiene                                                            crosspolymer.sup.32)                         43    78/16/6                                                                              16      Dimethicone Copolyol.sup.13)                                                              Cysteamine soln., 37.5% active               44    73/22/5                                                                              22      Cetyl Dimethicone                                                                         Cysteamine soln., 37.5% active                                    Copolyol.sup.12)                                         45    70/20/10                                                                             20      Cetyl Dimethicone                                                                         Cysteamine, 8.25% active                                          Copolyol.sup.12)                                         46    45/45/10                                                                             45      Cetyl Dimethicone                                                                         Hair Reducing Base No. 2.sup.31)                                  Copolyol.sup.12)                                         47    45/45/10                                                                             45      Dimethicone Copolyol.sup.13)                                                              Hair Reducing Base No. 2.sup.31)             48    63/27/10                                                                             27      Dimethicone Copolyol.sup.13)                                                              Hair Reducing Base No. 2.sup.31)             49    63/27/10                                                                             27      Cetyl Dimethicone                                                                         Hair Reducing Base No. 2.sup.31)                                  Copolyol.sup.12)                                         50    45/45/10                                                                             45      Cetyl Dimethicone                                                                         Hair Reducing Base No. 2.sup.31)                                  Copolyol.sup.12)                                         51    45145/10                                                                             45      Dimethicone Copolyol.sup.13)                                                              Hair Oxidizing Base (2.2%                                                     hydrogen peroxide)                           52    63/27/10                                                                             27      Dimethicone Copolyol.sup.13)                                                              Hair Oxidizing Base (2.2%                                                     hydrogen peroxide)                           53    63/27/10                                                                             27      Cetyl Dimethicone                                                                         Hair Oxidizing Base (2.2%                                         Copolyol.sup.12)                                                                          hydrogen peroxide)                           54    70/20/10                                                                             20      Cetyl Dimethicone                                                                         Hair Oxidizing Base (2.2%                                         Copolyol.sup.12)                                                                          hydrogen peroxide)                           55    70/20/10                                                                             20      Cetyl Dimethicone                                                                         1% aqueous red dye solution                                       Copolyol.sup.12)                                                                          (Tri-K Arianor Madder Red)                   56    70/20/10                                                                             20      Cetyl Dimethicone                                                                         1% aqueous yellow dye solution                                    Copolyol.sup.12)                                                                          (Tri-K Arianor Straw Yellow)                 57    70/20/10                                                                             20      Cetyl Dimethicone                                                                         1% aqueous blue dye solution                                      Copolyol.sup.12)                                                                          Tri-K Arianor Steel Blue)                    58    70/20/10                                                                             20      Dimethicone Copolyol.sup.13)                                                              1% aqueous red dye solution                                                   (Tri-K Arianor Madder Red)                   59    70/20/10                                                                             20      Dimethicone Copolyol.sup.13)                                                              1% aqueous yellow dye solution                                                (Tri-K Arianor Straw Yellow)                 60    82/10/8                                                                              10      Cetyl Dimethicone                                                                         FD&C Blue #1 Dye (5%)                                             Copolyol.sup.12) (50%) and                                                    Stearoxy Dimethicone                                                          (50%).sup.24)                                            61    72/18.7/9.3                                                                          18.7    Cetyl Dimethicone                                                                         FD&C Blue #1 Dye (10%)                                            Copolyol.sup.12)                                         62    72/18.7/9.3                                                                          18.7    Cetyl Dimethicone                                                                         FD&C Red #22 Dye (10%)                                            Copolyol.sup.12)                                         63    7/2/1  20      Cetyl Dimethicone                                                                         1% aqueous sunscreen solution                                     Copolyol.sup.12)                                                                          (Benzophenone-4)                             64    74/17.2/8.8                                                                          17.2    Cetyl Dimethicone                                                                         5% aqueous sunscreen solution                                     Copolyol.sup.12) (60%) and                                                                (benzophenone-4)                                                  Stearoxy Dimethicone                                                          (40%).sup.24)                                            65    82.5/10.8/6.7                                                                        10.8    Cetyl Dimethicone                                                                         5% aqueous sunscreen solution                                     Copolyol.sup.12)                                                                          (benzophenone-4)                             66    77.7/13.8/8.5                                                                        13.8    Cetyl Dimethicone                                                                         10% aqueous optical brightener                                    Copolyol.sup.12)                                                                          solution (Stilbene derivative).sup.26)       67    78.5/14/7.5                                                                          14      Dimethicone Copolyol.sup.13)                                                              5% aqueous protein solution                                                   (hydrolyzed keratin).sup.33)                 68    80.2/13.5/6.3                                                                        13.5    Cetyl Dimethicone                                                                         25% aqueous humectant                                             Copolyol.sup.12)                                                                          solution (sodium PCA).sup.34)                69    81.5/10.4/8.1                                                                        10.4    Cetyl Dimethicone                                                                         25% aqueous humectant                                             Copolyol.sup.12) (55%) and                                                                solution (sodium PCA).sup.34)                                     Dimethicone Copolyol.sup.35)                                                  (45%)                                                    70    87/9.8/3.2                                                                           9.8     Cetyl Dimethicone                                                                         25% aqueous humectant                                             Copolyol.sup.12)                                                                          solution (sodium PCA).sup.34)                71    80.5/13.3/6.2                                                                        13.3    Cetyl Dimethicone                                                                         50% humectant solution                                            Copolyol.sup.12)                                                                          (glycerin)                                   72    78/14.5/7.5                                                                          14.5    Cetyl Dimethicone                                                                         10% humectant solution                                            Copolyol.sup.12)                                                                          (glycolic acid)                              73    78.7/14.2/7.1                                                                        14.2    Cetyl Dimethicone                                                                         aqueous phase include 2%                                          Copolyol.sup.12)                                                                          FD&C Red #40 dye and 13%                                                      Polyquaternium-11 hair fixative                                               resin.sup.16)                                74    50/40/10                                                                             40      Cetyl Dimethicone                                                                         20% aqueous solution of a hair                                    Copolyol.sup.12)                                                                          fixative resin                                                                (Polyquaternium-11).sup.16)                  75    70/20/10                                                                             20      Cetyl Dimethicone                                                                         20% aqueous solution of a hair                                    Copolyol.sup.12)                                                                          fixative resin                                                                (Polyquaternium-11).sup.16)                  76    70/20/10                                                                             20      Cetyl Dimethicone                                                                         20% aqueous solution of a hair                                    Copolyol.sup.12)                                                                          fixative resin                                                                (Polyquaternium-11).sup.16)                  77    70/20/10                                                                             20      Cetyl Dimethicone                                                                         20% aqueous solution of a hair                                    Copolyol.sup.12)                                                                          fixative resin                                                    (Polyquaternium-11).sup.16)                              78    80/17/3                                                                              17      Cyclomethicone and                                                                        20% aqueous solution of a hair                                    Dimethicone Copolyol                                                                      fixative resin                                                    Blend.sup.37)                                                                             (Polyquaternium-11).sup.16)                  79    85/10/5                                                                              10      Dimethicone Copolyol.sup.13)                                                              20% aqueous solution of a hair                                                fixative resin                                                                (Polyquaternium-11).sup.16)                  80    85/10/5                                                                              10      Cetyl Dimethicone                                                                         20% aqueous solution of a hair                                    Copolyol.sup.12)                                                                          fixative resin                                                                (Polyquaternium-11).sup.16)                  81    87/10/3                                                                              10      Dimethicone Copolyol.sup.13)                                                              20% aqueous solution of a hair                                                fixative resin                                                                (Polyquaternium-11).sup.16)                  82    86.3/9.2/4.5                                                                         9.2     Cetyl Dimethicone                                                                         20% aqueous solution of a hair                                    Copolyol.sup.12)                                                                          fixative resin                                                                (Polyquaternium-11).sup.16)                  83    87/10/3                                                                              10      Dimethicone Copolyol.sup.13)                                                              20% aqueous solution of a hair                                                fixative resin                                                                (Polyquaternium-11).sup.16)                  84    78.9/14.6/6.5                                                                        14.6.sup.37)                                                                          Cetyl Dimethicone                                                                         20% aqueous solution of a hair                            (hydrocarbon)                                                                         Copolyol.sup.12)                                                                          fixative resin                                                                (Polyquaternium-11).sup.16)                  85    80/12.6/7.4                                                                          12.6.sup.37)                                                                          Cetyl Dimethicone                                                                         20% aqueous solution of a hair                            (hydrocarbon)                                                                         Copolyol.sup.12)                                                                          fixative resin                                                                (Polyquaternium-11).sup.16)                  86    80/12.6/7.4                                                                          12.6.sup.37)                                                                          Cetyl Dimethicone                                                                         20% aqueous solution of a hair                            (hydrocarbon)                                                                         Copolyo.sup.12) (50%) and                                                                 fixative resin                                                    Laureth-4 (50%)                                                                           (Polyquaternium-11).sup.16)                  87    80/10/10                                                                             10.sup.38)                                                                            ABIL WE-09.sup.40)                                                                        D&C Red #40 Dye (2%)                                      Cetyl                                                                         Dimethicone.sup.39)                                                           (nonvolatile                                                                  silicone)                                                        88    82/11.6/6.4                                                                          11.6.sup.38)                                                                          Cetyl Dimethicone                                                                         D&C Red #40 Dye (3%)                                      Cetyl   Copolyol.sup.12)                                                                          e,                                                        Dimethicone.sup.39)                                                           (nonvolatile                                                                  silicone)                                                        89    75/18/7                                                                              18.sup.38)                                                                            Cetyl Dimethicone                                                                         Glycolic Acid (10%)                                       Phenyl  Copolyol.sup.12)                                                      Trimethicone.sup.41)                                                          (nonvolatile                                                                  silicone                                                         __________________________________________________________________________    .sup.28) weight percent volatile silicone (cyclomethicone) or volatile        hydrocarbon in the                                                            primary W.sub.1 /O emulsion;                                                  .sup.29) FLEXAN 130, hair fixative resin, available from National Starch      & Chemical Corp., Bridgewater, NJ,                                            available as a 30% active material;                                           .sup.30) first topically-active compound incorporated into the internal       aqueous phase of the primary emulsion;                                        .sup.31) Hair Reducing Base No. 2 includes:                                     water              67.4 (wt. %)                                               ammonium thioglycolate (60% solution)                                                            23.0                                                       dithioglycolate (40% solution)                                                                    5.0                                                       ammonium hydroxide (28%)                                                                          2.1                                                       ammonium bicarbonate                                                                              2.0                                                       glycerin            0.5;                                                    .sup.32) GANTREZ ® XL-80, hair fixative resin, available from ISP         Chemicals, Inc., Wayne, NJ,                                                   added as a 5% active material;                                                .sup.33) CROTEIN HKP, available from Croda, Inc., NY, NY, as a 50% active     material;                                                                     .sup.34) AJIDEW N-50, available from Ajinomoto U.S.A., Inc., Teaneck, NJ,     as a 50% active material;                                                     .sup.35) DC Q2-5324, available from Dow Corning Corp., Midland, MI, as a      100% active material;                                                         .sup.36) AMERSIL ME358, available from Amerchol Corp., Edison, NJ, as a       100% active material;                                                         .sup.37) The cyclomethicone was replaced with a volatile hydrocarbon,         PERMETHYL 101A, available from                                                Presperse, Inc., South Plainfield, NJ;                                        .sup.38) The cyclomethicone was replaced by a nonvolatile silicone;           .sup.39) ABIL ® Wax 9801, available as a 100% active material from        Goldschmidt Chemical Co., Hopewell, VA;                                       .sup.40) a blend of polyglyceryl-4 isostearate, cetyl dimethicone             copolyol and hexyl laurate, available from Goldschmidt                        Chemical Co., Hopewell, VA; and                                               .sup.41) DOW CORNING 556 FLUID, available as a 100% active material from      Dow Corning Corp., Midland, MI.                                               __________________________________________________________________________

Each W₁ -O-W₂ multiple emulsion composition summarized in Table III wasstable for a definite time period. The multiple emulsion compositions ofExamples 36-89 were not optimized for long term stability. Therefore,the stability of the multiple emulsion compositions varied with theidentity and amount of composition ingredients, especially theemulsifiers, and with the manufacturing conditions. For example, byusing low shear and relatively low mixing speeds (e.g., about 100 toabout 200 rpm on a bench-scale mixer), the external aqueous phase wasable to emulsify the primary W₁ /O emulsion. In every Example 36-89, theoil phase (O) of the primary emulsion isolated the firsttopically-active compound in the internal water phase (W₁) from thecationic hair conditioners present in the external aqueous phase (W₂).

The dye present in the compositions of Examples 55-62 and 73 dyed thehair after the cyclomethicone evaporated. The compositions of Examples55-62 and 73 were non-staining to skin and equipment because the dyesare not present in the external aqueous phase. W₁ /O primary emulsiondroplets incorporating a water-soluble or water-dispersible dye wasobserved in magnified photographs of the compositions of Examples 55-59.Deposition of the dyes was observed by a color change in the hair afterapplication of the composition to the hair and hair drying. Depositionof the sunscreen benzophenone-4 of Example 60 was detected on a woolswatch by measurement of the absorbance of ultraviolet light.

The compositions of Examples 87-89 utilize a nonvolatile siliconecompound as the oil phase. The first topically-active compound in eachcomposition was released by rubbing the treated hair after the treatedhair was rinsed.

As previously stated, two independent W₁ -O-W₂ multiple emulsioncompositions having different primary W₁ /O emulsions can be combinedwithout commingling of internal aqueous phases until after depositionand evaporation of the volatile oil phase. This was demonstrated in atest wherein two different primary emulsions were prepared. The firstprimary emulsion incorporated a red dye in the internal aqueous phase.The second primary emulsion incorporated a blue dye in the internalaqueous phase. Each primary emulsion was added to individual portions ofan external aqueous phase to provide two independent W₁ -O-W₂ multipleemulsion compositions. The two multiple emulsion compositions then werecombined. The dye-containing droplets of the two primary emulsions weredistinct and did not coalesce, commingle or transfer dyes when viewedthrough a microscope.

The following Examples 90-105 illustrate other-primary W₁ /O emulsionsthat have been prepared. Each of these primary emulsions can beincorporated into an external aqueous phase comprising a surfactantcapable of forming a layer of lamellar liquid crystals as the emulsifierto provide a W₁ -O-W₂ multiple emulsion composition of the presentinvention.

In Examples 90 through 105, the volatile oil phase was cyclomethicone(DOW CORNING 344 FLUID). The surfactant phase of the primary W₁ /Oemulsion was a combination of laureth-1 and laureth-4. In preparing thecompositions of Examples 90 through 105, the cyclomethicone, laureth-1and laureth-4, in a weight ratio of 70:20:10, respectively, were admixeduntil homogeneous. The internal aqueous phase comprised water, the firsttopically-active compound and sugar. The aqueous phase was 80% by weightof the primary emulsion. The sugar was an optional ingredient includedin the internal aqueous phase to match the refractive index of theaqueous phase to the refractive index of the volatile organic phase, andthereby provide a transparent primary W₁ /O emulsion in most cases.

Admixing the aqueous phase with the solution of the volatile oil phaseand the surfactant phase provided a clear, stable primary (W₁ /O)emulsion. Table IV summarizes the final weight percent of eachingredient present in the primary emulsions Of Examples 90 through 105,the final use of the composition, and the stability of the primaryemulsion.

                                      TABLE IV                                    __________________________________________________________________________       Internal Aqueous Phase    Volatile                                                 First Topically-                                                                        % Topically-                                                                             Organic Phase                                                                         Surfactant Phase                            %    effective effective                                                                           %    %       %    %    Composition                    Ex.                                                                              Sugar.sup.42)                                                                      compound  compound                                                                            Water                                                                              Cyclomethicone                                                                        Laureth-1                                                                          Laureth-4                                                                          Product Type                                                                             Stability           __________________________________________________________________________    90 36.4 Hyaluronic acid                                                                         0.13  44.1 13.6    3.88 1.94 Skin conditioner                                                                         stable              91 29.0 Sodium salicylate                                                                       3.90  47.0 14.0    4.00 2.00 Skin conditioner                                                                         stable              92 31.8 Urea      7.60  47.1 9.49    2.70 1.35 Skin conditioner                                                                         stable              93 35.5 85% lactic acid                                                                         4.90  45.0 10.2    2.93 1.46 Skin conditioner                                                                         stable              94 33.4 5% glycerin                                                                             3.60  46.8 11.3    3.24 1.62 Skin conditioner                                                                         stable              95 32.2 Vitamin C 4.29  45.1 12.9    3.69 1.84 water-soluble                                                                            stablen             96 35.3 Vitamin B.sub.1                                                                         0.59  45.0 13.4    3.83 1.92 water-soluble                                                                            stablen             97 34.3 Pyridoxine                                                                              1.32  45.1 13.5    3.87 1.94 water-soluble                                                                            stablen                     hydrochloride                                                         98 37.1 Panthenol 1.90  46.3 10.3    2.95 1.47 water-soluble                                                                            stablen             99 35.7 Nicotinic acid                                                                          0.42  44.5 13.6    3.88 1.94 cosmetic   stable              100                                                                              35.7 Boric acid                                                                              1.08  43.8 13.7    3.90 1.95 medicament stable              101                                                                              34.9 Sodium    2.74  48.5 9.70    2.77 1.39 bacteriocide                                                                             stable                      sulfactamide                                                          102                                                                              32.5 Triclosan 1.03  37.6 20.2    5.77 2.88 bacteriocide                                                                             stable              103                                                                              37.6 Indomethacin                                                                            1.90  43.4 12.8    2.91 1.43 anti-inflammatory                                                                        stable              104                                                                              39.1 87% bisabolol                                                                           0.70  45.1 10.6    3.03 1.51 anti-irritant                                                                            stable              105                                                                              31.9 Silver sulfadiazine                                                                     3.30  36.8 19.6    5.61 2.81 medicament stable              __________________________________________________________________________     .sup.42) All % are by weight of the primary W.sub.1 /O emulsion.         

Each composition of Examples 90-105 can be incorporated in a W₁ -O-W₂multiple emulsion composition of the present invention, wherein theexternal aqueous phase further comprises a skin cleanser or a skinconditioner. The skin cleanser cleans the skin and is removed from theskin during a rinsing step. The skin conditioner is allowed to remain onthe skin. The first topically-active compound remains on the skin toperform its intended function after evaporation of the cyclomethicone.

The compositions of the following Examples 106 and 107 are leave-on W₁-O-W₂ multiple emulsion compositions. Each composition was applied tothe skin, then allowed to remain on the skin without a rinsing step. Ineach example, the skin care products in the external aqueous (W₂) phaseperform their intended function upon application to the skin. Afterevaporation of the water in the external aqueous phase, and evaporationof the volatile oil phase of the primary W₁ /O emulsion, the firsttopically-active compound, or compounds, in the aqueous phase (W₁) ofthe primary emulsion is released to contact the skin and perform itsintended function.

Each W₁ -O-W₂ multiple emulsion composition of Examples 106 and 107 wasprepared by the above-described two-step method, wherein the primary W₁/O emulsion and the external aqueous phase are prepared independently,then the primary W₁ /O emulsion and the external aqueous phase arecombined to form the multiple emulsion composition. The W₁ -O-W₂multiple emulsion compositions of Examples 106 and 107 are stabilized bya layer of lamellar liquid crystals.

    ______________________________________                                        EXAMPLE 106                                                                   ______________________________________                                        Primary W.sub.1 /O emulsion                                                                           20%.sup.43)                                             water-58.5%.sup.44)                                                           glycolic acid.sup.45) -5%                                                     glycerin.sup.45) -12%                                                         cyclomethicone.sup.46) -17%                                                   silicon-based surfactant.sup.12) -7.5%                                      External aqueous (W.sub.2) phase.sup.43)                                      Soft Water              q.s. to 100%                                          Methyl paraben.sup.47)  0.12%                                                 Glycerin.sup.48)        2.4%                                                  Tetrasodium ethylenediamine-                                                                          0.08%                                                 tetraacetic acid                                                              Triethanolamine         0.8%                                                  Ester blend.sup.49)     2.64%                                                 CRODAMOL PMP.sup.50)    0.54%                                                 C.sub.12 -C.sub.15 alkyl benzoate                                                                     0.264%                                                Stearic acid            2.64%                                                 Cetearyl alcohol        0.64%                                                 Cetyl palmitate         0.44%                                                 GLUCAM E-20 distearate.sup.51)                                                                        0.4%                                                  ARLACEL 165.sup.52)     0.4%                                                  SILICONE 593 fluid.sup.53)                                                                            0.08%                                                 DMDM Hydantoin.sup.47)  0.2%                                                  Fragrance               0.08%                                                 Dye                     0.00008%                                              ______________________________________                                         .sup.43) percent by weight in the W.sub.1 --O--W.sub.2 multiple emulsion      composition;                                                                  .sup.44) percent by weight in the primary (W.sub.1 /O) emulsion;              .sup.45) firsttopically active compound;                                      .sup.46) volatile oil phase;                                                  .sup.47) preservative;                                                        .sup.48) secondtopically active compound;                                     .sup.49) blend of tridecyl stearate, neopentyl glycol                         dicaprylate/dicaparate and tridecyl trimellitate, available as a 100%         active material from Lipo Chemicals, Inc., Paterson, NJ;                      .sup.50) PPG2-myristyl ether propionate, available as a 100% active           material from Croda, Inc., NY, NY;                                            .sup.51) PEG20 methyl glucose distearate, available as a 100% active          material from Amerchol Corp., Edison, NJ;                                     .sup.52) glyceryl stearate and PEG100 stearate blend, available as a 100%     active material from ICI Americas, Wilmington, DE; and                        .sup.53) dimethicone trimethylsiloxysilicate, available as a 100% active      material from Dow Corning Corp., Midland, MI.                            

    ______________________________________                                        EXAMPLE 107                                                                   ______________________________________                                        Primary W.sub.1 /O emulsion                                                                           20%.sup.43)                                             water-48.6%.sup.44)                                                           glycerin.sup.45) -25%                                                         red dye.sup.45) -1%                                                           cyclomethicone.sup.46) -18%                                                   silicon-based surfactant.sup.12) -7.4%                                      External aqueous (W.sub.2) phase.sup.43)                                      Soft Water              q.s. to 100%                                          Methyl paraben.sup.47)  0.12%                                                 Glycerin.sup.48)        3.2%                                                  Tetrasodium ethylenediamine-                                                                          0.08%                                                 tetraacetic acid                                                              Ester blend.sup.49)     2.92%                                                 CRODAMOL PMP.sup.52)    1.68%                                                 GLUCATE SS.sup.44)      1.68%                                                 PROMULGEN D.sup.3)      0.84%                                                 GLUCAMATE SSE-20        0.84%                                                 CASTOR WAX MP-70.sup.56)                                                                              0.84%                                                 Cetearyl alcohol        0.54%                                                 Cetyl palmitate         0.42%                                                 SOLULAN C-24.sup.55)    0.28%                                                 SILICONE 593 fluid.sup.53)                                                                            0.17%                                                 Triethanolamine         0.24%                                                 Fragrance               0.008%                                                DMDM Hydantoin.sup.47)  0.24%                                                 ______________________________________                                         .sup.54) Methyl glucose sesquistearate, available as a 100% active            material from Americhol Corp., Edison, NJ;                                    .sup.55) a blend of choleth24 and ceteth24, available as a 100% active        material from Amerchol Corp., Edison, NJ; and                                 .sup.56) hydrogenated castor oil, available from CasChem, Bayonne, NJ.   

The compositions of Examples 106 and 107 were stable W₁ -O-W₂ multipleemulsion compositions that effectively delivered the first and secondtopically-active compounds to the skin.

A W₁ -O-W₂ multiple emulsion composition of the present inventiondemonstrates excellent esthetic and functional properties, such as theability to treat the hair or skin with incompatible topically-activecompounds from a single composition. The present multiple emulsioncompositions also provide a more efficacious and economical delivery ofwater-soluble topically-active compounds. The compositions also arephase stable at room temperature for extended storage periods due toformation of a layer of lamellar liquid crystals around the primary W₁/O emulsion.

In addition, the present W₁ -O-W₂ multiple emulsion compositions havethe additional benefit of keeping a water-soluble, firsttopically-active compound in the internal aqueous phase from contactingindividuals that apply the multiple emulsion composition, or fromcontacting workplace articles, such as sinks and countertops. Thevolatility of the oil phase of the primary emulsion also can be selectedand adjusted for release of the first topically-active compound at apredetermined temperature range, e.g., at normal hair drying, at blowdrying or at curling iron temperatures.

It should be understood that the foregoing detailed description is givenmerely by way of illustration. Obviously, many modifications andvariations of the invention as hereinbefore set forth can be madewithout departing from the spirit and scope thereof and therefore onlysuch limitations should be imposed as are indicated by the appendedclaims.

What is claimed and desired to be secured by Letters Patent is:
 1. Awater-in-oil-in-water multiple emulsion composition comprising:(a) about40% to about 99% by weight of the composition of an external aqueousphase comprising: (i) water and (ii) about 0.1% to about 15% by weightof the external aqueous phase of a surfactant system capable of formingliquid crystals, wherein the surfactant system in the external phase isselected from the group consisting of a quaternary ammonium compoundhaving two long alkyl (C₈ -C₂₂) chains, a di-long chain alkyl (C₈ -C₂₂)amine, a long chain fatty (C₈ -C₂₂) alcohol, an ethoxylated fatty (C₈-C₂₂) alcohol, a double-tailed anionic surfactant, a double-tailedphospholipid, and mixtures thereof; and (b) about 1% to about 60% byweight of the composition of a primary emulsion, said primary emulsioncomprising:(i) about 1% to about 95% by weight of the primary emulsionof an aqueous phase comprising a topically-effective amount of a firsttopically-active compound and water, (ii) about 5% to about 95% byweight of the primary emulsion of an oil phase comprising a volatilesilicone compound, a nonvolatile silicone compound, a volatilehydrocarbon compound, a nonvolatile hydrocarbon compound, or a mixturethereof, and (iii) about 0.1% to about 20% by weight of the primaryemulsion of a surfactant phase comprising a silicon-free surfactant orsurfactant blend having an HLB value of about 10 or less, an oil-solublesilicon-based surfactant, an oil-soluble polymeric surfactant, or amixture thereof.
 2. The composition of claim 1 wherein the externalaqueous phase further comprises 0% to about 30% by weight of theexternal aqueous phase of a second topically-active compound.
 3. Thecomposition of claim 2 wherein the first topically-active compound andthe second topically-active compound are different compounds.
 4. Thecomposition of claim 2 wherein the first topically-active compound andthe second topically-active compound are identical compounds.
 5. Thecomposition of claim 2 wherein the first topically-active compound andthe second topically-active compound are incompatible compounds.
 6. Thecomposition of claim 2 wherein the second topically-active compound ispresent in an amount of about 0.1% to about 30% by weight of theexternal phase.
 7. The composition of claim 2 wherein the secondtopically-active compound is selected from the group consisting of ahair conditioner, a skin conditioner, a hair cleanser, a skin cleanser,a hair fixative, a hair dye, a hair growth promoter, a deodorant, a skincare compound, a permanent wave compound, a hair relaxer, a hairstraightener, an antibacterial compound, a topically-active drug, anantifungal compound, an anti-inflammatory compound, a topicalanesthetic, a sunscreen, a dermatitis medication, an acne preparation,an oxidizing agent, an antioxidant, an optical brightener, a hairbleaching agent, a hair reducing agent, an ultraviolet light absorber, asunburn reliever, a self-tanning compound, an anti-itch compound, andmixtures thereof.
 8. The composition of claim 2 wherein the firsttopically-active compound comprises a hair fixative resin, a hairreducing agent, a protein, an oxidizing agent, a water-soluble hair dye,a sunscreen a humectant, or an optical brightener, and the secondtopically-active compound comprises a cationic hair conditioner or ananionic hair cleanser.
 9. The composition of claim 8 wherein the hairfixative resin is selected from the group consisting of apolyvinylpyrrolidone, Polyquaternium-11,PVP/dimethylaminoethylmethacrylate copolymer, a sodium polystyrenesulfonate, a polyethylene glycol, and mixtures thereof.
 10. Thecomposition of claim 2 wherein the first topically-active compoundcomprises a cationic hair conditioner, a deodorant, a skin care product,a bacteriocide, a topical medicament or a mixture thereof, and thesecond topically-active compound comprises an anionic cleanser.
 11. Thecomposition of claim 2 wherein the first topically-active compoundcomprises a neutralizer for reducing agents and the secondtopically-active compound comprises a reducing agent for permanent hairwaving, cysteine, cysteamine, or a hair conditioner.
 12. The compositionof claim 2 wherein the first topically-active compound comprises areducing agent for permanent hair waving, and the secondtopically-active compound comprises a hair cleanser or a hairconditioner.
 13. The composition of claim 2 wherein the firsttopically-active compound comprises a hair conditioner, and the secondtopically-active compound comprises an oxidizing agent.
 14. Thecomposition of claim 2 wherein the first topically-active compoundcomprises a topical medicament and the second topically-active compoundcomprises a topical anesthetic.
 15. The composition of claim 2 whereinthe first topically-active compound comprises a skin conditioner and thesecond topically-active compound comprises a make-up remover.
 16. Thecomposition of claim 2 wherein the first topically-active compoundcomprises a sunburn reliever, a sunscreen, a skin conditioner, abacteriocide, a deodorant, an antifungal compound, an anesthetic, ananti-inflammatory, an anti-irritant, an anti-itch compound, amedicament, a self-tanning compound, a dermatitis medication, or amixture thereof, and the second topically-active compound comprises askin cleanser.
 17. The composition of claim 2 wherein the firsttopically-active compound comprises a self-tanning compound, and thesecond topically-active compound comprises a skin conditioner.
 18. Thecomposition of claim 2 wherein the first topically-active compoundcomprises a hair conditioner, a hair dye, a hair growth promoter, a hairbleaching agent, or a mixture thereof, and the second topically-activecompound comprises a hair cleanser.
 19. The composition of claim 2wherein the first topically-active compound comprises a hair dye, andthe second topically-active compound comprises a hair conditioner, ableaching agent, or a mixture thereof.
 20. The composition of claim 2wherein the first topically-active compound comprises a water-solublehair conditioner and the second topically-active compound comprises asubstantive hair conditioner.
 21. The composition of claim 2 wherein thefirst topically-active compound comprises a sunscreen, a protein, ahumectant, or a mixture thereof, and the second topically-activecompound comprises a hair conditioner.
 22. The composition of claim 1wherein the external aqueous phase is free of a polymeric gelling agent.23. The composition of claim 1 wherein the composition is a liquidhaving a viscosity of about 1 to about 15,000 centipoise.
 24. Thecomposition of claim 1 wherein the composition is a cream having aviscosity of about 50,000 to about 1,200,000 centipoise and the externalaqueous phase is free of a polymeric gelling agent.
 25. The compositionof claim 1 wherein the primary emulsion is present in the form ofdroplets having a diameter of about 5 to about 1000 microns.
 26. Thecomposition of claim 1 wherein the first topically-active compound ispresent in an amount of about 0.1% to about 30% by weight of the primaryemulsion.
 27. The composition of claim 1 wherein the firsttopically-active compound is water soluble.
 28. The composition of claim1 wherein the first topically-active compound is selected from the groupconsisting of a hair conditioner, a skin conditioner, a hair cleanser, askin cleanser, a hair fixative, a hair dye, a hair growth promoter, adeodorant, a skin care compound, a permanent wave compound, a hairrelaxer, a hair straightener, an antibacterial compound, atopically-active drug, an antifungal compound, an anti-inflammatorycompound, a topical anesthetic, a sunscreen, a dermatitis medication, anacne preparation, an oxidizing agent, an antioxidant, an opticalbrightener, a hair bleaching agent, a hair reducing agent, anultraviolet light absorber, a sunburn reliever, a self-tanning compound,an anti-itch compound, and mixtures thereof.
 29. The composition ofclaim 1 wherein the oil phase is present in an amount of about 0.5% toabout 80% by weight of the primary emulsion.
 30. The composition ofclaim 1 wherein the oil phase comprises a volatile silicone compound.31. The composition of claim 30 wherein the volatile silicone compoundhas a viscosity of about 0.5 to about 6 centistokes.
 32. The compositionof claim 31 wherein the volatile silicone compound is a cyclomethicone.33. The composition of claim 1 wherein the oil phase comprises avolatile hydrocarbon compound having about 10 to about 30 carbon atoms.34. The composition of claim 33 wherein the volatile hydrocarboncompound has about 12 to about 24 carbon atoms and has a boiling pointat 760 mm of about 100° C. to about 250° C.
 35. The composition of claim1 wherein the oil phase comprises a nonvolatile silicone compound. 36.The composition of claim 1 wherein the oil phase comprises a nonvolatilehydrocarbon compound.
 37. The composition of claim 1 wherein the oilphase comprises a volatile oil phase and a nonvolatile oil phase. 38.The composition of claim 1 wherein the surfactant phase is present in anamount of about 0.1% to about 10% by weight of the primary emulsion. 39.The composition of claim 1 wherein the surfactant phase comprises asilicon-free surfactant or surfactant blend having an HLB of about 1 toabout
 7. 40. The composition of claim 1 wherein the surfactant phasecomprises one silicon-free surfactant having an HLB value of about 0.1to about
 10. 41. The composition of claim 1 wherein the surfactant phasecomprises a silicon-free surfactant blend having an HLB value of about 1to about 10, said surfactant blend comprising a first surfactant havingan HLB value of about 0.1 to about 10 and a second surfactant having anHLB greater than about
 10. 42. The composition of claim 1 wherein thesurfactant phase comprises a silicon-free nonionic surfactant selectedfrom the group consisting of a polyoxyethylene ether of a fatty (C₆-C₂₂) alcohol, a polyoxyethylene/polyoxypropylene ether of a fatty (C₆-C₂₂) alcohol, an ethyoxylated alkylphenol, a polyethylene glycol etherof methyl glucose, a polyethylene ether of sorbitol, and mixturesthereof.
 43. The composition of claim 1 wherein the surfactant phasecomprises an oil-soluble silicon-based surfactant.
 44. The compositionof claim 43 wherein the silicon-based surfactant comprises a dimethiconecopolyol having 15 or less total monomer units of ethylene oxide,propylene oxide or a mixture thereof, an alkyl dimethicone copolyolhaving the structure: ##STR4## wherein p is a numeral from 7 through 17;q is a numeral from 1 through 100;m is a numeral from 1 through 40; n isa numeral from 0 through 200; and PE is (C₂ H₄ O)_(a) (C₃ H₆ O)_(b) -Hhaving a molecular weight of about 250 to about 2000, wherein a and bare selected such that the weight ratio of C₂ H₄ O/C₃ H₆ O is from 100/0to 20/80, or a mixture thereof.
 45. The composition of claim 1 whereinthe surfactant phase comprises an oil-soluble polymeric surfactantcapable of forming water-in-oil emulsions and having repeating ethoxyunits, propoxy units, butoxy units or combinations thereof, and includesless than 40 weight % ethoxy units.
 46. The composition of claim 1wherein the surfactant phase comprises an oil-soluble silicon-basedsurfactant, and the oil phase comprises a volatile silicone compound ora nonvolatile silicone compound.
 47. The composition of claim 1 whereinthe surfactant phase comprises a silicon-free nonionic surfactant or anoil-soluble polymeric surfactant and the oil phase comprises a volatilehydrocarbon compound or nonvolatile hydrocarbon compound.
 48. Thecomposition of claim 1 wherein the oil phase comprises a combination ofa silicone compound and hydrocarbon compound, and the surfactant phasecomprises a combination of a silicon-based surfactant and a silicon-freenonionic surfactant, an oil-soluble polymeric surfactant or a mixturethereof.
 49. The composition of claim 1 wherein the surfactant system inthe external phase is present in an amount of about 0.1% to about 15% byweight of the external phase.
 50. A water-in-oil-in-water multipleemulsion composition comprising:(a) about 50% to about 95% by weight ofthe composition of an external aqueous phase comprising:(i) about 0.1%to about 30% by weight of the external aqueous phase of a secondtopically-active compound, (ii) about 0.5% to about 16% by weight of theexternal aqueous phase of a surfactant system capable of forming liquidcrystals, wherein the surfactant system in the external phase isselected from the group consisting of a quaternary ammonium compoundhaving two long alkyl (C₈ -C₂₂) chains, a di-long chain alkyl (C₈ -C₂₂)amine, a long chain fatty (C₈ -C₂₂) alcohol, an ethoxylated fatty (C₈-C₂₂) alcohol, a double-tailed anionic surfactant, a double-tailedphospholipid, and mixtures thereof; and (iii) water; and (b) about 5% toabout 50% by weight of the composition of a primary emulsion, saidprimary emulsion comprising:(i) about 10% to about 95% by weight of theprimary emulsion of an aqueous phase comprising (A) water and (B) about0.1% to about 30% by weight of the primary emulsion of a firsttopically-active compound; (ii) about 0.5% to about 80% by weight of theprimary emulsion of an oil phase comprising a volatile siliconecompound, a nonvolatile silicone compound, a volatile hydrocarboncompound, a nonvolatile hydrocarbon compound, or a mixture thereof, and(iii) about 0.1% to about 15% by weight of the primary emulsion of asurfactant phase comprising a silicon-free surfactant or surfactantblend having an HLB value of about 1 to about 7, an oil-solublesilicon-based surfactant, an oil-soluble polymeric surfactant, or amixture thereof.
 51. A water-in-oil-in-water multiple emulsioncomposition comprising:(a) about 40% to about 99% by weight of thecomposition of an external aqueous phase comprising: (i) water and (ii)about 0.001% to about 14.85% by weight of the composition of asurfactant system capable of forming liquid crystals, wherein thesurfactant system in the external phase is selected from the groupconsisting of a quaternary ammonium compound having two long alkyl (C₈-C₁₂) chains, a di-long chain alkyl (C₈ -C₂₂) amine, a long chain fatty(C₈ -C₂₂) alcohol, an ethoxylated fatty (C₈ -C₂₂) alcohol, adouble-tailed anionic surfactant, a double-tailed phospholipid, andmixtures thereof; and (b) about 1% to about 60% by weight of thecomposition of a primary emulsion, said primary emulsion comprising:(i)about 0.01% to about 57% by weight of the composition of an aqueousphase comprising water and about 0.001% to about 17.1% by weight of thecomposition of a first topically-active compound, (ii) about 0.005% toabout 57% by weight of the composition of an oil phase comprising avolatile silicone compound, a nonvolatile silicone compound, a volatilehydrocarbon compound, a nonvolatile hydrocarbon compound, or a mixturethereof, and (iii) about 0.001% to about 12% by weight of thecomposition of a surfactant phase comprising a silicon-free surfactantor surfactant blend having an HLB value of about 10 or less, anoil-soluble silicon-based surfactant, an oil-soluble polymericsurfactant, or a mixture thereof.
 52. The composition of claim 51wherein the external phase further comprises 0% to about 30% by weightof the composition of a second topically-active compound.
 53. A methodof treating the skin or hair with a topically-active compound comprisingtopically applying an effective amount of a water-in-oil-in-watermultiple emulsion composition to skin or hair, said compositioncomprising:(a) about 40% to about 99% by weight of the composition of anexternal aqueous phase comprising: (i) water and (ii) about 0.1% toabout 15% by weight of the external phase of a surfactant system capableof forming liquid crystals, wherein the surfactant system in theexternal phase is selected from the group consisting of a quaternaryammonium compound having two long alkyl (C₈ -C₂₂) chains, a di-longchain alkyl (C₈ -C₂₂) amine, a long chain fatty (C₈ -C₂₂) alcohol, anethoxylated fatty (C₈ -C₂₂) alcohol, a double-tailed anionic surfactant,a double-tailed phospholipid, and mixtures thereof; and (b) about 1% toabout 60% by weight of the composition of a primary water-in-oilemulsion, said primary emulsion comprising:(i) about 1% to about 95% byweight of the primary emulsion of an aqueous phase comprising atopically-effective amount of a first topically-active compound andwater, (ii) about 0.5% to about 95% by weight of the primary emulsion ofan oil phase comprising a volatile silicone compound, a nonvolatilesilicone compound, a volatile hydrocarbon compound, a nonvolatilehydrocarbon compound, or a mixture thereof, and (iii) about 0.1% toabout 20% by weight of the primary emulsion of a surfactant phasecomprising a silicon-free surfactant or surfactant blend having an HLBvalue of about 10 or less, an oil-soluble silicon-based surfactant, anoil-soluble polymeric surfactant, or a mixture thereof, wherein dropletsof the primary emulsion remain in contact with the skin or hair.
 54. Awater-in-oil-in-water multiple emulsion composition comprising:(a) about40% to about 99% by weight of the composition of an external aqueousphase comprising: (i) water and (ii) about 0.1% to about 15% by weightof the external aqueous phase of a surfactant system capable of formingliquid crystals, wherein the surfactant system in the external phase isselected from the group consisting of a mixture of cetyl alcohol,stearyl alcohol, dicetyldimmonium chloride,searylamidopropyldimethylamine and ceteareth-20; a mixture ofdistearyldimmonium chloride, cetrimonium chloride, cetyl alcohol andstearyl alcohol; a mixture of oleth-15, cetyl alcohol and stearylalcohol; and mixtures thereof; and (b) about 1% to about 60% by weightof the composition of a primary emulsion, said primary emulsioncomprising:(i) about 1% to about 95% by weight of the primary emulsionof an aqueous phase comprising a topically-effective amount of a firsttopically-active compound and water, (ii) about 5% to about 95% byweight of the primary emulsion of an oil phase comprising a volatilesilicone compound, a nonvolatile silicone compound, a volatilehydrocarbon compound, a nonvolatile hydrocarbon compound, or a mixturethereof, and (iii) about 0.1% to about 20% by weight of the primaryemulsion of a surfactant phase comprising a silicon-free surfactant orsurfactant blend having an HLB value of about 10 or less, an oil-solublesilicon-based surfactant, an oil-soluble polymeric surfactant, or amixture thereof.
 55. A water-in-oil-in-water multiple emulsioncomposition comprising:(a) about 40% to about 99% by weight of thecomposition of an external aqueous phase comprising: (i) water and (ii)about 0.1% to about 15% by weight of the external aqueous phase of asurfactant system capable of forming liquid crystals, wherein thesurfactant system in the external phase is selected from the groupconsisting of dicetyldimonium chloride, distearyldimonium chloride,di-palmitylamine, cetyl alcohol, stearyl alcohol, steareth-2,steareth-21, dioctylsodium sulfosuccinate, phosphatidylserine,phosphatidylcholine, and mixtures thereof; and (b) about 1% to about 60%by weight of the composition of a primary emulsion, said primaryemulsion comprising:(i) about 1% to about 95% by weight of the primaryemulsion of an aqueous phase comprising a topically-effective amount ofa first topically-active compound and water, (ii) about 5% to about 95%by weight of the primary emulsion of an oil phase comprising a volatilesilicone compound, a nonvolatile silicone compound, a volatilehydrocarbon compound, a nonvolatile hydrocarbon compound, or a mixturethereof, and (iii) about 0.1% to about 20% by weight of the primaryemulsion of a surfactant phase comprising a silicon-free surfactant orsurfactant blend having an HLB value of about 10 or less, an oil-solublesilicon-based surfactant, an oil-soluble polymeric surfactant, or amixture thereof.